Title of Invention	COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE
Abstract	The invention relates to catalytically bleaching substrates, especially laundry fabrics, with atmospheric oxygen or air. A method of bleaching a substrate is provided that comprises applying to the substrate, in an aqueous medium, an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by atmospheric oxygen. Also provided is a bleaching composition comprising, in an aqueous medium, atmospheric oxygen and an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by the atmospheric oxygen, wherein the aqueous medium is substantially devoid of peroxygen bleach or a peroxy-based or generating bleach system.

Title of Invention

COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE

Abstract

The invention relates to catalytically bleaching substrates, especially laundry fabrics, with atmospheric oxygen or air. A method of bleaching a substrate is provided that comprises applying to the substrate, in an aqueous medium, an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by atmospheric oxygen. Also provided is a bleaching composition comprising, in an aqueous medium, atmospheric oxygen and an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by the atmospheric oxygen, wherein the aqueous medium is substantially devoid of peroxygen bleach or a peroxy-based or generating bleach system.

Full Text	FORM -2 THE PATENTS ACT, 1970 (39 OF 1970) COMPLETE SPECIFICATION (See Section 10; rule 13) 1. TITLE OF INVENTION COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE 2. HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913, and having its registered office at Hindustan Lever House, 165/166 Backbay Reclamation, Mumbai -400 020, Maharashtra, India The following specification particularly describes the nature of the invention and the manner in which it is to be performed. COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE This invention relates to compositions and methods for catajytically bleaching substrates with atmospheric oxygen. Peroxygen bleaches are well known for their ability to remove stains from substrates. Traditionally, the substrate is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides. Generally, these systems must be activated. One method of activation is to employ wash temperatures of 60°C or higher. However, these high temperatures often lead to inefficient cleaning, and can also cause premature damage to the substrate. A preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United States laundry bleach products are typically based on sodium nonanoyloxybenzenesulphonate (SNOBS) as the organic precursor coupled with sodium perborate. Precursor systems are generally effective but still exhibit several disadvantages. For example,oganic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting in high capital costs. Also, precursor systems have large formulation space requirements so that a significant proportion of a laundry powder must be devoted to the bleach components, leaving less room for other active ingredients and complicating the development of concentrated powders. Moreover, precursor systems do not bleach very efficiently in countries where consumers have WO 00/12667 PCT/GB99/02876 wash habits entailing low dosage, short wash times, cold temperatures and low wash liquor to substrate ratios. Alternatively, or additionally, hydrogen peroxide and peroxy systems, can be activated 5 by bleach catalysts, such as by complexes of iron and the ligand N4Py (i. e. N. N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine) disclosed in W095/34628. or the ligand Tpen (i.e. N, N, N\ N"-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in W097/48787. According to these publications, molecular oxygen may be used as the oxidant as an alternative to peroxide generating systems. However, no role in catalysing 10 bleaching by atmospheric oxygen in an aqueous medium is reported. It has long been thought desirable to be able to use atmospheric oxygen (air) as the source for a bleaching species, as this would avoid the need for costly hydroperoxyl generating systems. Unfortunately, air as such is kinetically inert towards bleaching 15 substrates and exhibits no bleaching ability. Recently some progress has been made in this area. For example, WO 97/38074 reports the use of air for oxidising stains on fabrics" by bubbling air through an aqueous solution containing an aldehyde and a radical initiator. A broad range of aliphatic, aromatic and heterocyclic aldehydes is reported to be useful, particularly para-substituted aldehydes such as 4-methyl-, 4-ethyl- and 4- 20 isopropyl benzaldehyde, whereas the range of initiators disclosed includes N- hydroxysuccinimide, various peroxides and transition metal coordination complexes. However, although this system employs molecular oxygen from the air, the aldehyde component and radical initiators such as peroxides are consumed during the bleaching 25 process. These components must therefore be included in the composition in relatively high amounts so as not to become depleted before completion of the bleaching process in the wash cycle. Moreover, the spent components represent a waste of resources as they can no longer participate in the bleaching process. 30 Accordingly, it would be desirable to be able to provide a bleaching system based on atmospheric oxygen or air that does not rely primarily on hydrogen peroxide or a WO 00/12667 PCT/GB99/02876 hydroperoxyl generating system, and that does not require the presence of organic components such as aldehydes that are consumed in the process. Moreover, it would be desirable to provide such a bleaching system that is effective in aqueous medium. 5 We have surprisingly found that the long held wish to use atmospheric oxygen or air for bleaching substrates can be fulfilled without the attendant disadvantages referred to above. This has now been achieved by means of an organic substance that catalyses bleaching of the substrate by atmospheric oxygen, using the composition and method in accordance with the present invention. 10 Accordingly, in a first aspect, the present invention provides a bleaching composition comprising, in an aqueous medium, atmospheric oxygen and an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by the atmospheric oxygen, wherein the aqueous medium is substantially 15 devoid of peroxygen bleach or a peroxy-based or -generating bleach system. The medium is therefore preferably insensitive or stable to catalase, which acts on peroxy species, In a second aspect, the present invention provides a method of bleaching a substrate 20 comprising applying to the substrate, in an aqueous medium, an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by atmospheric oxygen. Furthermore, in a third aspect, the present invention provides the use of an organic 25 substance which forms a complex with a transition metal as a catalytic bleaching agent for a substrate in an aqueous medium substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, the complex catalysing bleaching of the substrate by the atmospheric oxygen. 30 Advantageously, the method according to the present invention permits all or the majority of the bleaching species in the medium (on an equivalent weight basis) to be WO 00/12667 PCT/GB99/02876 derived from atmospheric oxygen. Thus, the medium can be made wholly or substantially devoid of peroxygen bleach or a peroxy-based or generating bleach system. Furthermore, the organic substance is a catalyst for the bleaching process and, as such, is not consumed but can continue to participate in the bleaching process. The 5 catalytically activated bleaching system of the type in accordance with the present invention, which is based on atmospheric oxygen, is therefore both cost-effective and environmentally friendly. Moreover, the bleaching system is operable under unfavourable wash conditions which 10 include low temperatures, short contact times and low dosage requirements. Furthermore, the method is effective in an aqueous medium and is therefore particularly applicable to bleaching of laundry fabrics. Therefore, whilst the composition and method according to the present invention may be used for bleaching any suitable 15 substrate, the preferred substrate is a laundry fabric. The bleaching method may be carried out by simply leaving the substrate in contact with the medium for a sufficient period of time. Preferably, however, the aqueous medium on or containing the substrate is agitated. 20 The organic substance may comprise a preformed complex of a ligand and a transition metal. Alternatively, the organic substance may comprise a free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate. The organic substance may also be included in the form 25 of a composition of a free ligand or a transition metal-substitutable metal-ligand complex, and a source of transition metal, whereby the complex is formed in situ in the medium. " The organic substance forms a complex with one or more transition metals, in the latter 30 case for example as a dinuclear complex. Suitable transition metals include for example: manganese in oxidation states II-V, iron I-IV, copper I-III, cobalt I-III, nickel WO 00/12667 PCT/GB99/02876 I-III, chromium II-VII, silver I-II. titanium II-IV. tungsten IV-VI. palladium II, ruthenium II-V, vanadium II-V and molybdenum II-VL In a preferred embodiment, the organic substance forms a complex of the general 5 formula (Al): in which: 10 15 L represents a ligand as herein defined, or its protonated or deprotonated analogue; "X represents a coordinating species selected from any mono, bi or tri charged anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate manner, preferably selected from 20 and more preferably selected from 25 Y represents any non-coordinated counter ion, preferably selected from and BF4", and more preferably selected from 30 WO 00/12667 PCT/GB99/02876 R, R", R", R"" independently represent a group selected from hydrogen, hydroxyl. -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaiyl or carbonyl derivative group), -OAr. alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaiyl and carbonyl derivative groups, each of R, Ar, alkyl. alkenyl, cycloalkyl, 5 heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen, wherein E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups, and preferably R. R\ 10 R", R" represent hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or C1-4-alkyl; a represents an integer from 1 to 10, preferably from 1 to 4; k represents an integer from 1 to 10; n represents zero or an integer from 1 to 10, preferably from 1 to 4; IS m represents zero or an integer from 1 to 20, preferably from 1 to 8. Preferably, the ligand L is of the general formula (BI): Tl-[-Zl-(Ql)r-]s-22-(Q2)g-T2 20 Rl R2 wherein g represents zero or an integer from 1 to 6; r represents an integer from 1 to 6; 25 s represents zero or an integer from 1 to 6; Zl and Z2 independently represent a heteroatom or a heterocyclic or heteroaromatic ring, Zl and/or Z2 being optionally substituted by one or more functional groups E as defined below; 30 Ql and Q2 independently represent a group of the formula: WO 00/12667 PCT/GB99/02876 5 wherein 10>d+e+f>l; d=0-9; e=0-9; f=0-9; each Yl is independently selected from -0-, -S-, -SO-, -SO2-, -(G1)N-, -(G1)(G2)N- (wherein G1 and G2 are as defined below), -C(O)_, arylene, alkylene, 10 heteroarylene, -P- and -P(O)-; if s>l, each -[-Zl(Rl)-(Ql)r]- group is independently defined; Rl, R2, R6, R7, R8, R9 independently represent a group selected from 15 hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl. aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 20 and independently R8 together with R9 represent oxygen; E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from hydroxy, mono- or polycarboxylate derivatives, aryl, heteroaryl, sulphonate, thiol (-RSH), thioethers (-R-S-R"), disulphides (-RSSR"), 25 dithiolenes, mono- or polyphosphonates, mono- or polyphosphates, electron donating groups andUlectron withdrawing groups, and groups of formulae (G"XG^N-, (G"XG2) (G3)N-, (GlXG2)N-C(O)- G3O- and G3C(O) wherein each of G1 G2 and G3 is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoing)); 30 or one of R1-R9 is a bridging group bound to another moiety of the same general formula; WO 00/12667 PCT/GB99/02876 Tl and T2 independently represent groups R4 and R5, wherein R4 and R5 are as defined for R1-R9, and if g=0 and sX), Rl together with R4, and/or R2 together with RS, may optionally independently represent =CH-R10, wherein R10 is as defined for 5 Rl-R9,or Tl and T2 may together (-T2-T1-) represent a covalent bond linkage when s>l andg>0; if Zl and/or Z2 represent N and Tl and T2 together represent a single bond 10 linkage and Rl and/or R2 are absent, Q1 and/or Q2 may independently represent a group of the formula: =CH-[-Yl-]e-CH=, optionally any two or more of Rl, R2, R6, R7, R8. R9 independently are linked together by a covalent bond; 15 if Zl and/or Z2 represents O, then Rl and/or R2 do not exist; If Zl and/or Z2 represents S, N, P, B or Si then Rl and/or R2 may be absent; if Zl and/or Z2 represents a heteroatom substituted by a functional group E then Rl and/or R2 and/or R4 and/or RS may be absent. 20 The groups Zl and 72 preferably independently represent an optionally substituted heteroatom selected from N, P, O, S, B and Si or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidines, pyrazine, pyramidine, pyrazole, pyrrole, imidazole, benzimidazole, 25 quinoleine, isoquinoline, carbazole, indole, isoindole, furane, thiophene, oxazole and thiazole. " The groups R1-R9 are preferably independently selected from -H, hydroxy-C0-C20-alkyl, haIo-C0-C20-alkyl, nitroso, formyl-C0-C20-alkyl, carboxyl-C0-C20-alkyl and esters and 30 salts thereof, carbamoyl-C0-C20-alkyl, sulpho-C0-C20-alkyl and esters and salts thereof, sulphamoyl-C0-C20-alkyl, amino-C0-C20-alkyl, aryl-C0-C20-alkyl, heteroaryl-C0-C20- WO 00/12667 PCT/GB99/02876 alkyl, C0-C20-alkyl, alkoxy-C0-C8-alkyl. carbonyl-C0-C6-alkoxy, and aryl-C0-C6-alkyl and C0-C20-alkylamide. S One of R1-R9 may be a bridging group which links the ligand moiety to a second ligand moiety of preferably the same general structure. In this case the bridging group may have the formula -C-(R1l)(R12)-(D)p-Cm(R11(R12)- bound between the two moieties, wherein p is zero or one, D is selected from a heteroatom or a heteroatom-containing group, or is part of an aromatic or saturated homonuclear and heteronuclear 10 ring, n is an integer from 1 to 4, m" is an integer from 1 to 4. with the proviso that n"+m" 15 hetero atoms, in the same moiety, with the bridging group preferably being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge. In a first variant according to formula (BI), the groups Tl and T2 together form a single bond linkage and s>l, according to general formula (BII): 20 wherein Z3 independently represents a group as defined for Zl or 22; R3 independently represents a group as defined for R1-R9; Q3 independently represents a group as 25 defined for Ql, Q2; h represents zero or an integer from 1 to 6; and s"=s-l. WO 00/12667 PCT/GB99/02876 In a first embodiment of the first variant, in general formula (BIT), s"=l, 2 or 3; r=g=h=l; d=2 or 3; e=f=0; R6=R7=H, preferably such that the ligand has a general formula selected from: 10 15 20 and more preferably selected from: 25 30 In these preferred examples, Rl, R2, R3 and R4 are preferably independently selected from -H, alkyl, aryl, heteroaryl, and/or one of Rl -R4 represents a bridging group bound to another moiety of the same general formula and/or two or more of R1-R4 together represent a bridging group linking N atoms in the same moiety, with the bridging group WO 00/12667 PCT/GB99/02876 being alkylene or hydroxy-alkylene or a heteroaiyl-containing bridge, preferably heteroarylene. More preferably, Rl, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with 5 the bridging group being alkylene or hydroxy-alkylene. According to this first embodiment, in the complex preferably: 10 RCOO"; 15 In a second embodiment of the first variant, in general formula (BIT), s"=2; r=g=h=l; d=f=0; e=l; and each Yl is independently alkylene or heteroarylene. The ligand preferably has the general formula: 20 wherein A1,"A2, A3, A4 are independently selected from C1-9-alkylene or heteroarylene 25 groups; and N1 and N2 independently represent a hetero atom or a heteroarylene group. WO 00/12667 PCT/GB99/02876 In a preferred second embodiment, N1 represents an aliphatic nitrogen. N2 represents a heteroarylene group, Rl, R2, R3, R4 each independently represent -H, alkyl, aryl or heteroaryl, and A1, A2, A3, A4 each represent -CH2-. 5 One of R1-R4 may represent a bridging group bound to another moiety of the same general formula and/or two or more of R1-R4 may together represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge. Preferably, Rl, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyi, nitrogen-containing heteroaryl, 10 or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxy-alkylene. Particularly preferably, the ligand has the general formula: 15 20 wherein Rl, R2 each independently represent -H, alkyl, aryl or heteroaryl. According to this second embodiment, in the complex [MaLkXn] Ym preferably: 25 M=Fe(II)-(III), Mn(IV), Cu(II), Co(II)-(III); x= CH3CN, OH2, cr, Br", OCN, N3 SCN; OH-, O2, PO43-, C6H5BO22-, RCOO-; Y= €1O4, BPh4", Br C1 , [FeCl4,]", PF6 , NO3"; a=1,2,3,4; 30 n=0,1,2,3,4,5,6,7,8,9; m=1,2,3,4; and k= 1,2,4. WO 00/12667 PCT/GB99/02876 In a third embodiment of the first variant, in general formula (BII), s-=2 and r=g=h=l, according to the general formula: 10 In this third embodiment, preferably each Z1-Z4 represents a heteroaromatic ring; e=f=0; d=l; and R7 is absent, with preferably R1=R2=R3=R4= 2,4.6-trimethyl-3-SO3Na-phenyl, 2,6-diCl-3(or 4)-SO3Na-phenyl. Alternatively, each Z1-Z4 represents N; R1-R4 are absent; both Q1 and Q3 represent =CH-[-Yl-]e-CH=; and both Q2 and Q4 represent-CH2-[-Yl-]n-CH2- Thus, preferably the ligand has the general formula: WO 00/12667 PCT/GB99/02876 wherein A represents optionally substituted alkylene optionally interrupted by a heteroatom; and n is zero or an integer from 1 to 5. 5 Preferably, R1-R6 represent hydrogen, nl and A= -CH2, -CHOH-, -CH2N(R)CH2- or -CH2CH2N(R)CH2CH2- wherein R represents hydrogen or alkyl, more preferably A= -CH2-, -CHOH- or -CH2CH2NHCH2CH2-. According to this third embodiment, in the complex [MaLkXn]Ym preferably: 10 M=Mn(II)r(IV),Co(II)-(III),Fe(II)-(III); X= CH3CN, OH2, CI", Br", OCN, N3, SCN, OH", O2- PO43-, C6H5BO22; RCOO"; Y= C1O4, BPh4", Br", C1", [FeCl4]", PF6 , NO3"; a=1,2,3,4; 15 n=0,1,2,3,4,5,6,7, 8,9; m=1,2,3,4; and k=1,2,4. In a second variant according to formula (BI), Tl and T2 independently represent groups 20 R4, R5 as defined for Rl -R9, according to the general formula (BIII): WO 00/12667 PCT/GB99/02876 Preferably, the ligand is selected from: In a first embodiment of the second variant, in general formula (Bill), s=l; r=l; g=0; d=f=l; e=l-4; Yl= -CH2-; and Rl together with R4, and/or R2 together with R5, independently represent "CH-R10, wherein R10 is as defined for R1-R9, In one example, R2 together with R5 represents =CH-R10, with Rl and R4 being two separate groups. Alternatively, both Rl together with R4, and R2 together with RS may independently represent =CH-R10. Thus, preferred ligands may for example have a structure selected from: WO 00/12667 PCT/GB99/02876 wherein Rl and R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, heteroaryl-C0-C20-alkyls, alkylaryl, aminoalkyl, alkoxy, more preferably Rl and R2 being selected from optionally substituted phenols, heteroaryl-C0-C2-alkyls, R3 and R4 5 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-Co-C2-alkyls. According to this first embodiment, in the complex [MaLk„] Ym preferably: M= Mn(II)-(IV), Co(II)-(III), Fe(III); 10 X= CH3CN, OH2, CI", Br, OCN, N3" SCN, OH-, O2", PO4,3- C6H5BO2.2" RCOO-; Y= C1O4, BPh4", Br C1," [FeCl4,]", PF6", NO3"; a= 1,2,3,4; n= 0,1,2,3,4,5,6,7,8,9; 15 m= 1,2,3,4; and k=l,2,4. In a second embodiment of the second variant, in general formula (BIII), s=l; r=l; g=0; d=f=l; e=l-4; Yl= -C(R"XR"), wherein R" and R" are independently as defined for 20 R1-R9. Preferably, the ligand has the general formula: The groups"Rl, R2, R3, R4, R5 in this formula are preferably -H or C0-C20-alkyl, n=0 or 1, R6 is -H, alkyl, -OH or -SH, and R7, R8, R9, R10 are preferably each independently selected from -H, C0-C20-alkyl, heteroaryl-C0-C20-alkyl, alkoxy-C0-C8-alkyl and amino-30 C0-C20-alkyl WO 00/12667 PCT/GB99/02876 According to this second embodiment, in the complex [MaLkXn] Ym preferably: M= Mn(II)-(IV), Fe(II)-(III). Cu(II), Co(II)-(III) X= CH3CN, OH2, CI, Br, OOP, N3 SCN OH", O2 PO43 C6H5BO22 RCOO"; 5 Y- C1O4 BPh4 Br", CI", [FeCU]", PF6 NO; -1,2.3,4; n=0,1,2,3,4; m= 0,1,2,3,4,5,6,7,8; and k=l,2,3,4. 10 More preferably, the ligand has the general formula: 20 In a third embodiment of the second variant, in general formula (BIII), s=0; g=l; d=e=0; f=l -4. Preferably, the ligand has the general formula: wherein Rl, R2, R3 are as defined for R2, R4, R5. 25 According to this third embodiment, in the complex [MaLkXn] Ym preferably: M= Mna(II)-(IV), Fe(II)(III), Cu(II), Co(III); X= CH3CN, OH2, CI", Br, OCW, N3 SOT, OH",O2 PO43", C6H5BO22-, RCOO"; WO 00/12667 PCT/GB99/02876 5 In a fourth embodiment of the second variant, the organic substance forms a complex of the general formula (A): 10 in which M represents iron in the II, III,IV or V oxidation state, manganese in the II. III. IV, VI or VII oxidation state, copper in the I, II or III oxidation state, cobalt in the II. Ill 15 or IV oxidation state, or chromium in the II-VI oxidation state; X represents a coordinating species; h represents zero or an integer in the range from 0 to 3; z represents the charge of the complex and is an integer which can be positive, zero or negative; 20 Y represents a counter ion, the type of which is dependent on the charge of the complex; q - z/[charge Y]; and L represents a pentadentate ligand of the general formula (B): 25 R1 R2 wherein each R1, R2 independently represents -R4-R5, WO00/12«67 PCT/GB99/02876 R3 represents hydrogen, optionally substituted alkyl. aryl or arylalkyl. or -R4-R5, each R4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and 5 each R5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl. The ligand L having the general formula (B), as defined above, is a pentadentate ligand. 10 By "pentadentate" herein is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex. In formula (B), one coordinating hetero atom is provided by the nitrogen atom in the methylamine backbone, and preferably one coordinating hetero atom is contained in . 15 each of the four R1 and R2 side groups. Preferably, all the coordinating hetero atoms are nitrogen atoms. The ligand L of formula (B) preferably comprises at least two substituted or unsubstituted heteroaryl groups in the four side groups. The heteroaryl group is 20 preferably a pyridin-2-yl group and, if substituted, preferably a methyl- or ethyl-substituted pyridin-2-yl group. More preferably, the heteroaryl group is an unsubstituted pyridin-2-yl group. Preferably, the heteroaryl group is linked to methylamine, and preferably to the N atom thereof, via a methylene group. Preferably, the ligand L of formula (B) contains at least one optionally substituted amino-alkyl side group, more 25 preferably two amino-ethyl side groups, in particular 2-(N-alkyl)amino-ethyl or 2-(N,N-dialkyl)amino-ethyl. Thus, in formula (B) preferably R1 represents pyridin-2-yl or R2 represents pyridin-2-yl-methyl. Preferably R2 or R1 represents 2-amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-30 (N,N-di(m)ethyl)amino-ethyl. If substituted, Rs preferably represents 3-methyl pyridin-2-yl. R3 preferably represents hydrogen, benzyl or methyl. WO 00/12667 PCT/GB99/02876 Examples of preferred ligands L of formula (B) in their simplest forms are: (i) pyridin-2-yl containing ligands such as: 5 N.N-bis(pyridin-2-yl-methyl)bis(pyridin-2-yl)methylamine; N,N-bis(pyrazol-l -yl-methyl)-bis(pyridin-2-yl)methylamine; N,N-bis(imidazol-2-yl-methyl)-bis(pyridin-2-yl)methylamine; N,N-bis(l,2,4-triazol-l-yl-methyl)-bis(pyridin-2-yl)methylamine; N,N-bis(pyridin-2-yl-methyl)-bis(pyrazol-l-yl)methylamine; 10 N,N-bis(pyridin-2-yl-memyl)-bis(imidazol-2-yl)methylamine; N,N-bis(pyridin-2-yl-methyl)-bis( 1,2,4-triazol-1 -yl)methylamine; N,N-bis(pyridin-2-yl-methyl)-l.l-bis(pyridin-2-yl)-l-aminoethane; N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-phenyl-1 -aminoethane; N,N-bis(pyrazol-1 -yl-methyl)-1.1 -bis(pyridin-2-yI)-1 -aminoethane; 15 N,N-bis(pyrazol-1 -yl-methyl)-1.1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane; N,N-bis(imidazol-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-l -aminoethane; N,N-bis(imidazol-2-yl-methyl)l ,1 -bis(pyridin-2-yl)-2-phenyl-l -aminoethane; N,N-bis(l,2,4-tria2ol-l-yl-methyl)-1,1-bis(pyridin-2-yl)-l-aminoethane; N,N-bis(l ,2,4-triazol-1 -yl-methyl)-1,1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane; 20 N,N-bis(pyridm-2-yl-methyl)-l,l-bis(pyrazol-l-yl)-l-aminoethane; N,N-bis(pyridin-2-yl-methyl)-1.1 -bis(pyrazol-1 -yl)-2-phenyl-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-l ,1 -bis(imidazol-2-yl)-l -aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(imidazol-2-yl)-2-phenyl-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-l,l-bis(l,2,4-triazol-l-yl)-l-aminoethane; 25 N,N-bis(pyridin-2-yl-methyl)l,l-bis(l,2,4-triazol-l-yl)-l-aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-1 -aminoethane; N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-l-aminohexane; N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-phenyl-l-aminoethane; N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-(4-sulphonic acid-phenyl)-l-30 aminoethane; N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-(pyridin-2-yl)-l-ammoethane; WO 00/12667 PCT/GB99/02876 N,N-bis(pyridin-2-yI-methyl)-l,l-bis(pyridin-2-yl)-2-(pyridin-3-yl)-l-aminoe N,N-bis(pyridin-2-yl-methyl)-l-bis(pyridin-2yl)-2-(pyridin-4-yl)-1-aminoethane N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-(1-alkyl-pyridinium-4-yl)-1-aminoethane; 5 N,N-bis(pyridin-2-yI-methyl)-1,1-bis(pyridin-2-yl)-2-(l-alkyl-pyridinium-3-yl)-1-aminoethane; N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-2-yl)-1 -aminoethane; 10 (ii) 2-amino-ethyl containing ligands such as: N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyridin-2-yl)methylamine; N,N-bis(2-(N-alkl)amino-ethyl)-bis(pyrazol-l-yl)methylarnine; N,N-bis(2-(N-alkyl)amino-ethyl)-bis(imidazol-2-yl)methylamine; N,N-bis(2-(N-alkyl)amino-ethyl)-bis(l ,2,4-triazol-l -yl)methylamine; 15 N,N-bis(2-(N,N-alkyl)amino-ethyl)-bis(pyridin-2-yl)methylarnine; N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(pyrazol-1 -yl)methylamine; N,N-bis(2-(N,N-alkyl)amino-ethyl)-bis(imidazol-2-yl)methylamine; N,N-bis(2-(N,N-alkyl)amino-ethyl)-bis(l,2,4-triazol-l-yl)methylamine; N,N-bis(pyridin-2-yl-methyl)-bis(2-amino-ethyl)methylamine; 20 N,N-bis(pyrazol-1 -yl-methyl)-bis(2-amino-ethyl)methylamine; N,N-bis(imidazol-2-yl-methyl)-bis(2-amino-ethyl)methylamine; N,N-bis(l,2,4-triazol-l-yl-methyl)-bis(2-amino-ethyl)methylamine. More preferred ligands are: 25 N,N-bis(pyridin-2-yl-methyl)bis(pyridin-2-yl)methylamine, hereafter referred to as N4Py. N,N-bis(pyridin-2-yl-methyl)-l ,1 -bis(pyridin-2-yl)-l -aminoethane, hereafter referred to as MeN4Py, N,N-bis(pridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-phenyl-l-aminoethane, hereafter 30 referred to as BzN4Py. WO 00/12667 PCT/GB99/02876 In an alternative fourth embodiment, the organic substance forms a complex of the general formula (A) including a ligand (B) as defined above, but with the proviso that R3 does not represent hydrogen. 5 In a fifth embodiment of the second variant, the organic substance forms a complex of the general formula (A) as defined above, but wherein L represents a pentadentate or hexadentate ligand of general formula (C): R1R1N-W-NR1R2 10 wherein each R1 independently represents -R3-V, in which R3 represents optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and IS thiazolyl; W represents an optionally substituted alkylene bridging group selected from -CH2CH2",CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2-, and -CH2-C10H6-CH2-; and R2 represents a group selected from R\ and alkyl, aryl and arylalkyl groups 20 optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N*(R4)3, wherein R4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether and alkenyl ether. 25 The ligand L having the general formula (C), as defined above, is a pentadentate ligand or, if R1=R-, can be a hexadentate Iigand. As mentioned above, by "pentadentate" is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex. Similarly, by "hexadentate1 is meant that six hetero atoms can in principle coordinate to the metal M ion. However, in this case it is believed that one of the arms will not be 30 bound in the complex, so that the hexadentate ligand will be penta coordinating. WO 00/12667 PCT/GB99/02876 In the formula (C), two hetero atoms are linked by the bridging group W and one coordinating hetero atom is contained in each of the three R1 groups. Preferably, the coordinating hetero atoms are nitrogen atoms. 5 The ligand L of formula (C) comprises at least one optionally substituted heteroaiyl group in each of the three R1 groups. Preferably, the heteroaiyl group is a pyridin-2-yl group, in particular a methyl- or ethyl-substituted pyridin-2-yl group. The heteroaiyl group is linked to an N atom in formula (C), preferably via an alkylene group, more preferably a methylene group. Most preferably, the heteroaiyl group is a 3-methyl-10 pyridin-2-yl group linked to an N atom via methylene. The group R2 in formula (C) is a substituted or unsubstituted alkyl, aryl or arylalkyl group, or a group R1. However, preferably R2 is different from each of the groups R1 in the formula above. Preferably, R2 is methyl, ethyl, benzyl. 2-hydroxyethyl or 2-15 methoxyethyl. More preferably, R2 is methyl or ethyl. The bridging group W may be a substituted or unsubstituted alkylene group selected from -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2-, and -CH2-C10H6-CH2- (wherein -C6H4-, -C6H10-, -C10H6- can be ortho-,para-, or 20 meta-C6C4-, -C6H10-, -C10H6-). Preferably, the bridging group W is an ethylene or 1,4-butylene group, more preferably an ethylene group. Preferably, V represents substituted pyridin-2-yl, especially methyl-substituted or ethyl-substituted pyridin-2-yI, and most preferably V represents 3-methyl pyridin-2-yl. 25 Examples of preferred ligands of formula (C) in their simplest forms are: N-methyl-N,NNN"-tris(3-memyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-ethyl-N,N,NN"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 30 N-benzyl-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine; N-(2-hydroxyethyl)-N,N,,N,-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine WO 00/12667 PCT/GB99/02876 N-(2-methoxyethyl)-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-methyl-N,NN"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l,2diamine; N-ethyl-N,N,N"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; 5 N-benzyl-N,N",N"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine; N-(2-hydroxyethyl)-N,N"N"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-(2-methoxyethyl)-N,NN"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1.2diamine; N-methyl-N,N,,N,-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine; 10 N-ethyl-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-benzyl-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l,2dimine; N-(2-hydroxyethyl)-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethy!ene-l,2-diamine; N-(2-methoxyethyl)-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; 15 N-methy!-N,N"Nl"-tris(5-ethyl-pyridin-2-ylmethyl)ethyIene-l,2-diamine; N-ethyl-N,N",N"-tris(5-ethyl-pyridin-2-ylmethyl)ethyIene-l,2-diamine; N-benzy1-N,N,N"-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; and N-(2-methoxyethyl)N,N,N"-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine. 20 More preferred ligands are: N-methyl-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-ethyl-N,NN"-tris(3-methyl-pyridin-2-yImethyl)ethyIene-l,2-diamine; N-benzyl-N,N"N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; N-(2-hydroxyethyl)-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-diamine; 25 and N-(2-methoxyethyl)-N,N",N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine The most preferred ligands are: N-methyl-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine; and 30 N-ethyl-N,N,N"-tris(3-methyl-pyridin)-2-ylmethyl)ethylene-l,2diamine. WO 00/12667 PCT/GB99/02876 Preferably, the metal M in formula (A) is Fe or Mn. more preferably Fe. Preferred coordinating species X in formula (A) may be selected from R6OH. NR63, R6CN, R6OO", R6S", R60", R6COO", OCN", SCN", N3",CN", F, Cl", Br", T, O2", NO3", 5 NO2, SO42-, SO32, PO43- and aromatic N donors selected from pyridines, pyrazines, pyrazoles, pyrroles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, with R6 being selected from hydrogen, optionally substituted alkyl and optionally substituted aryl. X may also be the species LMO or LMOO", wherein M is a transition metal and L is a ligand as defined above. The coordinating species X is preferably 10 selected from CH3CN, H2O, F, Cl, Br, OOH", R6COO", R6O", LMO", and LMOO" wherein R6 represents hydrogen or optionally substituted phenyl, naphthyl, or C1-C4 alkyl. The counter ions Y in formula (A) balance the charge z on the complex formed by the 15 ligand L, metal M and coordinating species X. Thus, if the charge z is positive, Y may be an anion such as R7COO", BPh4", ClO4, BF4", PF6", R7SO3", R7SO4", SO42- NO3", F, C1", Br",or 1", with R7 being hydrogen, optionally substituted alkyl or optionally substituted aryl. If z is negative, Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation. 20 Suitable counter ions Y include those which give rise to the formation of storage-stable solids. Preferred counter ions for the preferred metal complexes are selected from R7COO", CIO4", BET, PF6 R7SO3 (in particular CF3SO3"), R7SO4", SO42, NO3", F, CI", Br, and F, wherein R7 represents hydrogen or optionally substituted phenyl, 25 naphthyl or C1-C4 alkyl. It will be appreciated that the complex (A) can be formed by any appropriate means, including in situ formation whereby precursors of the complex are transformed into the active complex of general formula (A) under conditions of storage or use. Preferably, 30 the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species. Alternatively, the WO 00/12667 PCT/GB99/02876 catalyst may be formed in situ from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials. In one such example, the active catalyst may be formed in situ in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent Thus, for example, 5 if M is iron, an iron salt such as FeSO4 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex. In another such example, the ligand L, or a ligand L-generating species, can be mixed with metal M ions present in the substrate or wash liquor to form the active catalyst in situ. Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that 10 comprise the ligand L and can be substituted by metal M ions to form the active complex according the formula (A). Therefore, in alternative fourth and fifth embodiments, the organic substance is a compound of the general formula (D): 15 in which M" represents hydrogen or a metal selected from Ti, V, Co, Zn, Mg. Ca, Sr, Ba. 20 Na,K,and Li; X represents a coordinating species; a represents an integer in the range from 1 to 5; b represents an integer in the range from 1 to 4; c represents zero or an integer in the range from 0 to 5; 25 z represents the charge of the compound and is an integer which can be positive, zero or negative; Y represents a counter ion, the type of which is dependent on the charge of the compound; q = z/[charge Y]; and 30 L represents a pentadentate ligand of general formula (B) or (C) as defined above. WO 00/12667 PCT/GB99/02876 In a fourth embodiment of the first variant, the organic substance comprises a macrocyclic iigand of formula (E): 5 wherein Z1 and Z2 are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring 10 structure being substituted by one or more substituents; Y1 and Y2 are independently selected from C, N, O, Si, P and S atoms; A1 and A2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl) being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulphonate, phosphate, electron 15 donating groups and electron withdrawing groups, and groups of formulae (G1)G2)N-, G3OC(O) G3O- and G3C(O)-, wherein each of G1, G2 and G3 is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups (in addition to any amongst the foregoing); i and j are selected from1 and 2 to complete the valency of the groups Y1 and 20 Y2; each of Q1-Q4 is independently selected from groups of formula 25 wherein 10>a+b+O2 and d>=1; WO 00/12667 PCT/GB99/02876 each Y3 is independently selected from -0-. -S-, -SO-, -S02-, -(G1)N- (wherein G1 is hereinbefore defined), -C(O)- arylene, heteroarylene, -P- and -P(O)-; each of A3-A6 is independently selected from the groups hereinbefore defined for A1 and A2; and 5 wherein any two or more of Al-A6 together form a bridging group, provided that if A1 and A2 are linked without simultaneous linking also to any of A3-A6, then the bridging group linking A1 and A2 must contain at least one carbonyl group. In the ligands of formula (E), unless specifically stated to the contrary, all alkyl, 10 hydroxyalkyl alkoxy, and alkenyl groups preferably have from 1 to 6, more preferably from 1 to 4 carbon atoms. Moreover, preferred electron donating groups include alkyl (e.g. methyl), alkoxy (e.g. methoxy), phenoxy, and unsubstituted. monosubsthuted and disubstituted amine groups. 15 Preferred electron withdrawing groups include nitro. carboxy. sulphonyl and halo groups. The ligands of formula (E) may be used in the form of complexes with an appropriate metal or, in some cases, in non-complexed form. In the non-complexed form, they rely 20 upon complexing with a metal supplied in the form of a separate ingredient in the composition, specifically provided for supplying that metal, or upon complexing with a metal found as a trace element in tap water. However, where the ligand alone or in complex form carries a (positive) charge, a counter anion is necessary. The ligand or complex may be formed as a neutral species but it is often advantageous, for reasons of 25 stability or ease of synthesis, to have a charged species with appropriate anion. Therefore, in an alternative fourth embodiment, the ligand of formula (E) is ion-paired with a counter ion, which ion-pairing is denoted by formula (F): 30 WO 00/12667 PCT/GB99/02876 wherein H is an hydrogen atom; Y is a counter anion, the type of which is dependent on the charge of the complex; 5 x is an integer such that one or more nitrogen atoms in L is protonated; z represents the charge of the complex and is an integer which can be positive or zero; q=z/[charge of Y]; and L is a ligand of formula (E) as defined above. 10 In a further alternative fourth embodiment, the organic substance forms a metal complex of formula (G) based on the ion pairing of formula (F) thus: [Ms L]zYq 15 wherein L, Y, x, z and q are as defined for formula (F) above and M is a metal selected from manganese in oxidation states II-V, iron II-V, copper I-III, cobalt I-III, nickel I-III, chromium II-VI, tungsten IV-VI, palladium V, ruthenium II-IV, vanadium III-IV and molybdenum IV-VI. 20 Especially preferred are the complexes of formula (G) wherein M represents manganese, cobalt, iron or copper. In a preferred fourth embodiment, the organic substance forms a complex of the formula 25 (H): WO 00/12667 PCT/GB99/02S76 wherein M represents an Iron atom in oxidation state II or III. a manganese atom in oxidation state II, ID, IV or V, a copper atom in oxidation state I, II or III or a cobalt 5 atom in oxidation state n, III or IV, X is a group which is either a bridge or is not a bridge between iron atoms, Y is a counter ion, x and y being >=1,0= For the avoidance of doubt, ""==" means "greater than or equal to". 15 Preferably, in the complex of formula (H), M represents an iron atom in oxidation state II or III or aVanganese atom in oxidation state II, HI, IV, or V. Preferably the oxidation state of M is ,IIL 20 When M is iron, preferably the complex of formula (H) is in the form of a salt of iron (in oxidised state) dihalo-2,1 l-diazo[3.3](2,6)pyridinophane, dihalo-4-methoxy-2,l 1-diazo[3.3] (2,6) pyridinophane and mixtures thereof, especially in the form of the chloride salt . WO 00/12667 PCT/GB99/02876 When M is manganese, preferably the complex of formula (H) is in the form of a salt of manganese (in oxidised state) N, N"-dimethyl-2,1 l-diazo[3.3](2,6)pyridinophane, especially in the form of the monohexafiuorophosphate salt. Preferably, X is selected from H2O, Off, O2", SH, S2 SO42-NR9R10, RCOO", 5 NR9R10R11, CI", Br", F", N3 and combinations thereof, wherein R9, R10 and R11 are independently selected from -H, C1-4 alkyl and aryl optionally substituted by one or more electron withdrawing and/or donating groups. More preferably, X is a halogen, especially a fluoride ion. In the formulae (F), (G) and (H), the anionic counter ion equivalent Y is preferably 10 selected from CI", Br, I", N03, C104 SCN", PF6-, RS03 RS04", CF3S03 BPh4", and OAc A cationic counter ion equivalent is preferably absent. In formula (H), R1 and R2 are preferably both hydrogen. R3 and R4 are preferably C1-4 alkyl, especially methyl. R5-R8 are each preferably hydrogen. According to the values of x and y, the aforementioned preferred iron or manganese 15 catalysts of formula (H) may be in the form of a monomer, dimer or oligomer. Without being bound by any theory, it has been conjectured that in the raw materia! or detergent composition state, the catalyst exists mainly or solely in monomer form but could be converted to dimer, or even oligomeric form, in the wash solution. The bleaching compositions according to the present invention may be used for laundry 20 cleaning, hard surfaces cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.). As is generally known in the art, bleaching compositions are also employed waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact 25 lens disinfection. In the context of the present invention bleaching should be understood as relating generally to the decolonisation of stains or of other materials attached to or associated with a substrate. However, it is envisaged that the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to 30 or otherwise associated with a substrate. WO 00/12667 PCT/GB99/02876 In typical washing compositions the level of the organic substance is such that the in-use level is from l µM to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 µM. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching 5 Preferably, the aqueous medium has a pH in the range from pH 6 to 13, more preferably from pH 6 to 11, still more preferably from pH 8 to 11. and most preferably from pH 8 to 10, in particular from pH 9 to 10. 10 The bleaching composition of the present invention has particular application in detergent formulations, especially for laundry cleaning. Accordingly, in another preferred embodiment, the present invention provides a detergent bleach composition comprising a bleaching composition as defined above and additionally a surface-active material, optionally together with detergency builder. 15 The bleach composition according to the present invention may for example contain a surfacejactive material in an amount of from 10 to 50% by weight The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof. 20 Many suitable actives are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch. Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of 25 organic sulphates and sulphonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher aryl groups. Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium 30 alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride WO 00/12667 PCT/GB99/02876 sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of 5 fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C10) with sodium bisulphite and those derived by reacting paraffins with SO2 and Cl2 and then hydrolysing with a base to produce a random sulphonate; sodium and ammonium (C7-C12) dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe material made by reacting olefins, 10 particularly (C10-C20) alpha-olefins, with SO3 and then neutralising and hydrolysing the reaction product The preferred anionic detergent compounds are sodium (C10-C15) alkylbenzene sulphonates, and sodium (C16-C18) alkyl ether sulphates. Examples of suitable nonionic surface-active compounds which may be used, preferably 15 together with the anionic surface-active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally"5-25 EO, ie. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO. Other so-called nonionic surface-actives include 20 alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides. Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively 25 high cost. If any amphoteric or zwitterionic detergent compounds are used, it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives. The detergent bleach composition of the invention will preferably comprise from 1 to 15 30 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant. In a WO 00/12667 PCT/GB99/02876 further preferred embodiment, the detergent active system is free from C16-C12 fatty acid soaps. The bleach composition of the present invention may also contains a detergency builder, 5 for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof. 10 Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyioxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and 15 polyacetal carboxylates as disclosed in US-A-4,144.226 and US-A-4,146,495. Example"s of precipitating builder materials include sodium orthophosphate and sodium carbonate. 20 Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070. 25 In particular, the compositions of the invention may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts. Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyioxy malonate, carboxymethyioxy 30 succinate and water-insoluble crystalline or amorphous aluminositicate builder WO 00/12667 PCT/GB99/02876 materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder. It is preferred that the composition contains not more than 5% by weight of a carbonate 5 builder, expressed as sodium carbonate, more preferably not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10. Apart from the components already mentioned, the bleach composition of the present invention can contain any of the conventional additives in amounts of which such 10 materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkemel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted 15 alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e. Dequest® types); fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate and sodium silicate; and, usually in very small amounts, fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants. 20 Transition metal sequestrants such as EDTA, and phosphonic acid derivatives such as EDTMP (ethylene diamine tetra(methylene phosphonate)) may also be included, in addition to the organic substance specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided 25 the composition remains bleaching effective. However, the composition according to the present invention containing the organic substance, is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the organic substance). 30 Whilst the present invention is based on the catalytic bleaching of a substrate by atmospheric oxygen or air, it will be appreciated that small amounts of hydrogen WO 00/12667 PCT/GB99/02876 peroxide or peroxy-based or -generating systems may be included in the composition, if desired. Preferably, however, the composition will be devoid of peroxygen bleach or peroxy-based or -generating bleach systems. 5 The invention will now be further illustrated by way of the following non-limiting examples: WO 00/12667 PCT/GB99/02876 EXAMPLES Example 1 5 This example describes a synthesis of a catalyst according to formula (A): (i) Preparation of MeN4Py ligand: The precursor N4Py.HClO4 was prepared as follows: 10 To pyridyl ketone oxim (3 g, 15.1 mmol) was added ethanol (15 ml), concentrated ammonia solution (15 mL) and NH4OAC (1.21 g, 15.8 mmol). The solution was warmed until reflux. To this solution was added 4.64 g Zn in small portions. After the addition of all Zn, the mixture was refluxed for 1 hour and allowed to cool to ambient temperature. The solution was filtered and water (15 ml) was added. Solid NaOH was 15 added until pH» 10 and the solution was extracted with CH2Cl2 (3 x 20 ml). The organic layers were dried over Na2SO4 and evaporated until dryness. Bis(pyridin-2-yl)methylamme (2.39 g, 12.9 mmol) was obtained as a colourless oil in 86% yield, showing the following analytical characteristics: 1H NMR (360 MHz, CDCl3): δ 2.64 (s, 2H, NH2), 5.18 (s, 1H, CH), 6.93 (m, 2H, 20 pyridine), 7.22 (m, 2H, pyridine), 7.41 (m, 2H, pyridine), 8.32 (m, 2H, pyridine); ,3C NMR(CDC13): 5 62.19 (CH), 121.73 (CH), 122.01 (CH), 136.56 (CH), 149.03 (CH), 162.64 (Cq). To picolylchloride hydrochloride (4.06 g, 24.8 mmol) was added, at 0°C, 4.9 ml of a 5N 25 NaOH solution. This emulsion was added by means of a syringe to bis(pyridin-2-yl)methylamine (2.3 g, 12.4 mmol) at 0°C. Another 5 ml of a 5N NaOH solution was added to this mixture. After warming to ambient temperature, the mixture was stirred vigorously for 40 hrs. The mixture was put in an ice bath and HClO4 was added until pH WO 00/12667 PCT/GB99/02876 to ambient temperature, whereupon a light-brown solid precipitated which was collected by filtration and washed with cold water and air-dried (1.47 g). From 0.5 g of the perchlorate salt of N4Py prepared as described above, the free amine 5 was obtained by precipitating the salt with 2N NaOH and subsequently by extraction with CH2Cl2. To the free amine was added under argon 20 ml of dry tetrahydrofuran freshly distilled from LLAlH4. The mixture was stirred and cooled to -70 °C by an alcohol / dry ice bath. Now 1 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mixture was allowed to warm to -20 °G and 10 now 0.1 ml of methyl iodide was added. The temperature was kept to -10 °C for 1 hour. Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue water was added and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried on sodium sulphate, filtered and evaporated giving 0,4 g residue. The residue was purified by crystallisation from ethyl 15 acetate and hexane giving 0.2 g of creamish powder (50% yield) showing the following analytical characteristics: 1H NMR(400 MHz, CDCl3): δ (ppm) 2.05 (s, 3H, CH3), 4.01 (s, 4H, CH2), 6.92 (m, 2H, pyridine), 7.08 (m, 2H, pyridine), 7.39 (m, 4H pyridine), 7.60 (m 2H, pyridine), 7.98 (d, 2H, pyridine), 8.41 (m, 2H pyridine), 8.57 (m, 2H, pyridine). I3C NMR (100.55 20 MHz, CDCl3): 6 (ppm) 21.7 (CH3), 58.2 (CH2), 73.2 (Cq), 121.4 (CH), 121.7 (CH), 123.4 (CH), 123.6 (CH), 136.0 (CH), 148.2 (Cq), 148.6 (Cq), 160.1 (Cq), 163.8 (Cq). (ii) Synthesis of the complex l(MeN4Py)Fe(CH3CN)](C1O4)2, Fe(MeN4Py): 25 To a solution of 0.27 g of MeN4Py in 12 ml of a mixture of 6 ml acetonitrile and 6 ml methanol was added 350 mg Fe(C1O4)2.6H2O immediately a dark red colour formed. To the mix was added now 0.5 g of sodium perchlorate and a orange red precipitate formed immediately. After 5 minutes stirring and ultrasonic treatment the precipitate was isolated by filtration and dried in vacuo at 50°C. In this way 350 mg of an orange red 30 powder was obtained in 70% yield showing the following analytical characteristics: WO 00/12667 PCT/GB99/02876 39 1H NMR (400 MHz, CD3CN): 8 (ppm) 2.15, (CH3CN), 2.28 (s, 3H, CH3), 4.2 (ab, 4H, CH2), 7.05 (d, 2H, pyridine), 7.38 (m, 4H, pyridine), 7.71 (2t, 4H pyridine), 7.98 (t, 2H, pyridine), 8.96 (d, 2H pyridine), 9.06 (in, 2H, pyridine). UV/Vis (acetonitrile) [Xmax, nm (e, M"" cm-1)]: 381 (8400), 458 nm (6400). 5 Anal.Calcd for C25H26Cl2FeN6O8: C, 46.11; H, 3.87; N, 12.41; CI, 10.47; Fe, 8.25. Found: C, 45.49; H, 3.95; N, 12.5; CI, 10.7; Fe, 8.12. Mass-ESP (cone voltage 17V in CH3CN): m/z 218.6 [MeN4PyFe]2+; 239.1 [MeN4PyFeCH3CN2+. 10 Example 2 This example describes a synthesis of a catalyst according to formula (A): (i) Synthesis of BzN4Py ligand: 15 To 1 g of the N4Py ligand prepared as described above, 20 ml of dry tetrahydrofuran freshly distilled from L1AIH4, was added under argon. The mixture was stirred and cooled to -70 °C by an alcohol / dry ice bath. Now 2 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mix was allowed to warm 20 to -20°C and now 0.4 ml of benzyl bromidide was added. The mixture was allowed to warm up to 25 °C and stirring was continued over night Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue water was added and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried on sodium sulphate, filtered and evaporated giving 1 g 25 brown oily residue. According to NMR spectroscopy, the product was not pure but contained no starting material (N4Py). The residue was used without further purification. (ii) Synthesis of the complex [(BzN4Py)Fe(CH3CN)l(C104)j, Fe(BzN4Py): 30 To a solution of 0.2 g of the residue obtained by the previous described procedure in 10 ml of a mixture of 5 ml acetonitrile and 5 ml methanol was added 100 mg WO 00/12667 PCT/GB99;02876 40 Fe(ClO4)2.6H2O immediately a dark red colour formed. To the mix was added now 0.25 g of sodium perchlorate and ethylacetate was allowed to diffuse into the mixture overnight Some red crystals were formed which were isolated by filtration and washed with methanol. In this way 70 mg of a red powder was obtained showing the following 5 analytical characteristics: 1H NMR (400 MHz, CD3CN): 5 (ppm) 2.12, (s, 3H, CH3CN), 3.65 + 4.1 (ab, 4H, CH2), 4.42 (s, 2H, CH2-benzyl), 6.84 (d, 2H, pyridine), 7.35 (m, 4H, pyridine), 7.45 (m. 3 H, benzene) 7.65 (m, 4H benzene + pryidine), 8.08(m, 4H, pyridine), 8.95 (m, 4H pyridine). 10 UV/Vis (acetonitrile) [Xmax, nm (e, M"1 cm"1)]: 380 (7400), 458 nm (5500). Mass-ESP (cone voltage 17V in CH3CN): m/z 256.4 [BzN4Py]2+; 612 [BzN4PyFeC104]+ Example 3: 15 This example describes syntheses of catalysts according to formula (C): AH reactions were performed under a nitrogen atmosphere, unless indicated otherwise. All reagents and solvents were obtained from Aldrich or Across and used as received, 20 unless stated otherwise. Petroleum ether 40-60 was distilled using a rotavapor before using it as eluent Flash column chromatography was performed using Merck silica gel 60 or aluminium oxide 90 (activity II-III according to Brockmann).1H NMR (300 MHz) and 13C NMR (75 MHz) were recorded in CDCl3, unless stated otherwise. Multiplicities were addressed with the normal abbreviations using p for quintet. 25 Synthesis of.starting materials for ligand synthesis: Synthesis of N-benzyl amino acetonitrile. N-benzyl amine (5.35 g, 50 mmol) was dissolved in a water: methanol mixture (50 mL, 1:4). Hydrochloric acid (aq., 30 %) 30 was added until the pH reached 7.0. Added was NaCN (2.45 g, 50 mmol). After cooling to 0 °C, formaline (aq. 35 %, 4.00 g, 50 mmol) was added. The reaction was followed by TLC (aluminium oxide; EtOAc: Et3N = 9:1) until benzylamine could be WO 00/12667 PCT/GB99/02876 detected. Subsequently the methanol was evaporated in vacuo and the remaining oil "dissolved" in water. The aqueous phase was extracted with methylene chloride (3 x 50 mL). The organic layers were collected and the solvent removed in vacuo. The residue was purified by Kugelrohr distillation (p = 20 mm Hg, T = 120oG) giving N-benzyl 5 amino acetonitrile (4.39 g, 30 mmol, 60 %) as a colourless oil. 1H NMR: δ 7.37 - 7.30 (m, 5H), 3.94 (s, 2H), 3.57 (s, 2H), 1.67 (br s, 1H); 13C NMR: δ 137.74,128.58,128.46,128.37,127.98,127.62,117.60.52.24,36.19. Synthesis of TV-ethyl amino acetonitrile. This synthesis was performed analogously to 10 the synthesis reported for N-benzyl amino acetonitrile. However, detection was done by dipping the TLC plate in a solution of KMnO4 and heating the plate until bright spots appeared. Starting from ethylamine (2.25 g, 50 mmol), pure TV-ethyl amino acetonitrile (0.68 g, 8.1 mmol, 16 %) was obtained as a slightly yellow oil. lH NMR: δ 3.60 (s, 2H), 2.78 (q, J= 7.1,2H). 1.22 (br s, 1H), 1.14 (t, J= 7.2,3H); 15 ,3CNMR: δ117.78,43.08,37.01,14.53. Synthesis of TV-ethyl ethylene-l ,2-diamine. The synthesis was performed according to Hageman; J.Org.Chem.; 14; 1949; 616, 634, starting from N-ethyl amino acetonitrile. 20 Synthesis of TV-benzyl ethylene-l,2-diamine. Sodium hydroxide (890 mg; 22.4 mmol) was dissolved in ethanol (96 %, 20 mL), the process taking the better part of 2 hours. Added was N-benzyl amino acetonitrile (4,2.92 g, 20 mmol) and Raney Nickel (approx. 0.5 g). Hydrogen pressure was applied (p = 3.0 atm.) until hydrogen uptake ceased. The mixture was filtered over Cellite, washing the residue with ethanol. The filter 25 should not run dry since Raney Nickel is relatively pyrophoric. The Cellite containing the Raney Nickel was destroyed by putting the mixture in dilute acid, causing gas formation). The ethanol was evaporated in in vacuo and the residue dissolved in water. Upon addition of base (aq. NaOH, 5N) the product oiled out and was extracted with chloroform (3 x 20 mL). After evaporation of the solvent in vacuo the "H NMR showed 30 the presence of benzylamine. Separation was enforced by column chromatography (silica gel; MeOH: EtOAc: Et3N = 1:8:1) yielding the benzyl amine, followed by the WO 00/12667 PCT/GB99/02876 solvent mixture MeOH : EtOAc: Et3N = 5:4:1. Detection was done by using aluminium oxide as a solid phase in TLC, yielding pure N-benzyl ethylene-l,2-diamine (2.04 g, 13.6 mmol, 69%). 1H NMR: δ 733 - 7.24 (m, 5H), 3.80 (s, 2H), 2.82 (t, J= 5.7,2H), 2.69 (t J-= 5.7. 5 2H),1.46(brs,3H); 13C NMR: 8 140.37,128.22,127.93,126.73,53.73,51.88,41.66. Synthesis of 2-acetoxymethyl-5-methyl pyridine. 2,5-Lutidine (31.0 g, 290 mmol), acetic acid (180 mL) and hydrogen peroxide (30 mL, 30 %) were heated at 70-80 °C for 10 3hours. Hydrogen peroxide (24 mL, 30 %) was added and the subsequent mixture heated for 16 hours at 60-70 °C. Most of the mixture of (probably) hydrogen peroxide, water, acetic acid, and peracetic acid was removed in vacuo (rotavap, water bath 50 °C until p = 20 mbar). The resulting mixture containing the N-oxide was added dropwise to acetic anhydride heated under reflux. This reaction was highly exothermic, and was 15 controlled by the dropping speed. After heating under reflux for an hour, methanol was added dropwise. This reaction was highly exothermic. The resulting mixture was heated under reflux for another 30 minutes. After evaporation of the methanol (rotavap, 50 °C until p = 20 mbar), the resulting mixture was purified by Kugelrohr distillation (p = 20 mm Hg, T -150 °C). The clear oil that was obtained still contained acetic acid. 20 This was removed by extraction (CH2Cl2, NaHCO3 (sat)) yielding the pure acetate of 2-acetoxymethyl-5-methyI pyridine (34.35 g, 208 mmol, 72 %) as a slightly yellow oil. 1H NMR: δ 8.43 (s, 1H), 7.52 (dd, J = 7.8, J - 1.7,1H), 7.26 (d, J - 7.2,1H), 5.18 (s, 2H), 2.34 (s, 3H), 2.15 (s, 3H); 13CNMR: 8 170.09,152.32,149.39,136.74,131.98,121.14,66.31,20.39,17.66. 25 Synthesis of 2-acetoxymethyl-5-ethyl pyridine. This synthesis was performed analogously to the synthesis reported for 2-acetoxymethyl-5-methyl pyridine. Starting from 5-ethyl-2-methyl pyridine (35.10 g, 290 mmol), pure 2-acetoxymethyl-5-ethyl pyridine (46.19 g, 258 mmol, 89%) was obtained as a slightly yellow oil. 30 1HNMR: δ 8.47 (s, 1H), 7.55 (d, J= 7.8,1H), 7.29 (d, J= 8.1,1H), 2.67 (q, J= 7.8,2H), 2.14 (s, 3H), 1.26 (t, J= 7.77,3H); WO 00/12667 PCT/GB99/02876 13C NMR: 8 170.56,152.80,149.11,138.47,135.89,121.67,66.72.25.65,20.78, 15.13. Synthesis of 2-acetoxymethyl-3-methyl pyridine. This synthesis was performed 5 analogously to the synthesis reported for 2-acetoxymethyl-5-methyl pyridine. The only difference was the reversal of the Kugelrohr distillation and the extraction. According to lH NMR a mixture of the acetate and the corresponding alcohol was obtained. Starting from 2,3-picoline (31.0 g, 290 mmol), pure 2-acetoxymethyl-3-methyl pyridine (46.19 g, 258 mmol, 89%. calculated for pure acetate) was obtained as a slightly yellow 10 oil. 1HNMR: δ 8.45 (d, J= 3.9,1H), 7.50 (d, J= 8.4,1H), 7.17 (dd, J= 7.8, J=4.8, 1H), 5.24 (s, 2H), 2.37 (s, 3H), 2.14 (s, 3H). Synthesis of 2-hydroxymetbyl-5-methyl pyridine. 2-Acetoxymethyl-5-methyl 15 pyridine (30 g, 182 mmol) was dissolved in hydrochloric acid (100 mL. 4 N). The mixture was heated under reflux, until TLC (silica gel; triethylamine:ethyl acetate:petroleum ether 40-60 = 1:9:19) showed complete absence of the acetate (normally 1 hour). The mixture was cooled, brought to pH > 11, extracted with dichloromethane (3 x 50 mL) and the solvent removed in vacuo. Pure 2-20 hydroxymethyl-5-methyl pyridine (18.80 g, 152 mmol, 84 %) was obtained by Kugelrohr distillation (p = 20 mm Hg, T = 130 °C) as a slightly yellow oil. 1H NMR: δ 8.39 (s, 1H), 7.50 (dd, J= 7.8, J= 1.8,IH), 7.15 (d, J= 8.1,1H), 4.73 (s, 2H), 3.83 (br s, 1H), 2.34 (s, 3H); 13C NMR: 8 156.67,148.66,137.32,131.62,120.24,64.12,17.98. 25 Synthesis of 2-hydroxymethyl-5-ethyl pyridine. This synthesis was performed analogousr/to the synthesis reported for 2-hydroxymethyl-5-methyl pyridine. Starting from 2-acetoxymethyl-5-ethyl pyridine (40 g, 223 mmol), pure 2-hydroxymethyl-5-ethyl pyridine (26.02 g, 189 mmol, 85 %) was obtained as a slightly yellow oil. 30 1HNMR: δ 8.40(d, J=1.2, lH),7.52(dd, J=8.0, J=2.6, IH), 7.18 (d,J= 8.1, 1H), 4.74 (s, 2H), 3.93 (br s, 1H), 2.66 (q, J = 7.6,2H), 1.26 (t, J= 7.5,3H); WO 00/12667 PCT/GB99/02876 l3C NMR: 5 156.67,148.00,137.87,136.13,120.27,64.07,25.67,15.28. Synthesis of 2-hydroxymethyl-3-methyl pyridine. This synthesis was performed analogously to the synthesis reported for 2-hydroxymethyl-5-methyl pyridine. Starting from 2-acetoxymethyl-3-methyl pyridine (25g (recalculated for the mixture), 152 mmol), pure 2-hydroxymethyl-3-methyl pyridine (15.51 g, 126 mmol, 83 %) was obtained as a slightly yellow oil. 1H NMR: δ 8.40 (d, J=4.5, 1H)), 7.47 (d, J= 12,1H), 7.15 (dd, J- 7.5, J= 5.1, 1H), 4.85 (br s, 1H), 4.69 (s, 1H), 222 (s, 3H); 13CNMR: 8 156.06,144.97,137.38,129.53,121.91,61.38,16.30. (i) Synthesis of lieands: Synthesis of N-methyl-N,N,N,-tris(pyridin-2-ylmethyI)ethylene-l,2-diamine (L1). The ligand L1 (comparative) was prepared according to Bernal, Ivan; Jensen, Inge Margrethe; Jensen, Kenneth B.; McKenzie, Christine J.; Toftlund, Hans; Tuchagues, Jean-Pierre; J.Chem.Soc.DaIton Trans.; 22; 1995; 3667-3676. Synthesis of N-methyl-N,N,N,-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L2, MeTrilen). 2-Hydroxymethyl-3-methyI pyridine (5.00 g, 40.7 mmol) was dissolved in dichloromethane (30 mL). Thionyl chloride (30 mL) was added dropwise under cooling (ice bath). The resulting mixture was stirred for 1 hour and the solvents removed in vacuo (rotavap, until p= 20 mm Hg, T = 50 °C). To the resultant mixture was added dichloromethane (25 mL). Subsequently NaOH (5 N, aq.) was added dropwise until the pH (aqua) > 11. The reaction was quite vigorous in the beginning, since part of the thionyl chloride was still present N-methyl ethylene-1,2-diamine (502 mg, 6.8 mmol) and additional NaOH (5 N, 10 mL) were added. The reaction mixture was stirred at room temperature for 45 hours. The mixture was poured into water (200 mL), and the pH checked (> 14, otherwise addition of NaOH (aq. 5N)). The reaction mixture was extracted with dichloromethane (3 or 4 x 50 mL,-until no product could be detected by TLC). The combined organic phases were dried and the solvent WO 00/12667 PCT/GB99/02876 removed in vacuo. Purification was enforced as described before, yielding N-methyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine as a slightly yellow oil. Purification was enforced by column chromatography (aluminium oxide 90 (activity II-III according to Brockmann); triethylamine: ethyl acetate: petroleum either 40-60 -5 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf ~ 0.9). The compound was eluted using ethylacetate : triethyl amine = 9:1. N-memyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L2,1.743 g, 4.30 mmol, 63 %) was obtained. 1H NMR: δ 8.36 (d, J = 3.0,3H), 7.40 - 7.37 (m, 3H), 7.11 -7.06 (m, 3H), 3.76 (s, 10 4H), 3.48 (s, 2H), 2.76 - 2.71 (m, 2H), 2.53 - 2.48 (m, 2H), 2.30 (s, 3H), 2.12 (s, 6H), 2.05 (s,3H); 13C NMR: 8 156.82,156.77,145.83,145.67,137.61,133.14,132.72,122.10, 121.88,62.32,59.73,55.19,51.87,42.37,18.22,17.80. 15 Synthesis of N-ethyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L3, EtTrilen). This synthesis is performed analogously to the synthesis for L2. Starting from 2-hydroxymethyl-3-methyl pyridine (25.00 g, 203 mmol) and N-ethyl ethylene-1,2-diamine (2.99 g, 34.0 mmol), N-ethyl-N,N,N",tris(methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L3,11.49 g, 28.5 mmol, 84 %) was obtained. Column 20 chromatography (aluminium oxide; Et3N : EtOAc: petroleum ether 40-60 = 1:9:30, followed by Et3N: EtOAc = 1:9). 1H NMR: δ 8.34 - 8.30 (m, 3H), 7.40 - 7.34 (m, 3H), 7.09 - 7.03 (m, 3H), 3.71 (s, 4H), 3.58 (s, 2H), 2.64 - 2.59 (m, 2H), 2.52 - 2.47 (m, 2H), 2.43 - 2.36 (m, 2H), 2.31 (s, 3H), 2.10 (s, 6H), 0.87 (t, J= 72,3H); 25 13C NMR: , δ 157.35,156.92,145.65,137.61,133.14,132.97,122.09,121.85,59.81, 59.28,51.98; 50.75,48.02,18.27,17.80,11.36. Synthesis of N-benzyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L4, BzTrilen). This synthesis is performed analogously to the synthesis for 30 L2. Starting from 2-hydroxymethyI-3-methyIpyridine (3.00 g 24.4 mmol), and N-benzyl ethylene-1,2-diamine (610 mg, 4.07 mmol), N-benzyl-N,N,N"-tris(3-methylpyridin-2- WO 00/12667 PCT/GB99/02876 ylmethyl)ethylene-l,2-diamine (L4,1.363 g, 2.93 mmol, 72 %) was obtained. Column chromatography (aluminium oxide; Et3N: EtOAc: petroleum ether 40-60 = 1:9:10). 1H NMR: δ 8.33 - 8.29 (m, 3H), 7.37 - 7.33 (m, 3H), 7.21 - 7.03 (m, 8H), 3.66 (s, 4H), 3.60 (s, 2H), 3.42 (s, 2H), 2.72 - 2.67 (m, 2H), 2.50 - 2.45 (m, 2H),2 23 (s, 3H), 5 2.03 (s, 6H); 13C NMR: 8 157.17,156.96,145.83,145.78,139.29,137.91,137.80,133.45, 133.30,128.98,127.85,126.62,122/28,122.22,59.99,58.83,51.92,51.54.18.40, 17.95. 10 Synthesis of N-hydroxyethyl-N,NN"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L5). This synthesis is performed analogously to the synthesis for L6. Starting from 2-hydroxymethyl-3-methyl pyridine (3.49 g, 28.4 mmol), and N-hydroxyethyl ethylene-1,2-diamine (656 mg 6.30 mmol), after 7 days N"-hydroxyethyl-N,N,N"tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L5,379 mg, 0.97 mmol. 14 %) was 15 obtained. 1H NMR: δ 8.31 - 8.28 (m, 3H), 7.35 - 7.33 (m, 3H), 7.06 - 7.00 (m, 3H), 4.71 (br s, 1H), 3.73 (s, 4H), 3.61 (s, 2H), 3.44 (t, J= 5.1,2H), 2.68 (s, 4H), 2.57 (t, J= 5.0,2H), 2.19 (s,3H), 2.10 (s,6H); 13C NMR: 8 157.01,156.88,145.91,145.80,137.90,137.83,133.30,131.89, 20 122.30,121.97,59.60,59.39,57.95,56.67,51.95,51.22,18.14,17.95. Synthesis of iV-methyl-N,N,N"-tris(5-methylpyridin-2-yimethyl)ethylene-l^-diamine (L6). 2-hydroxymethyI-5-methyl pyridine (2.70 g, 21.9 mmol) was dissolved in dichloromethane (25 mL). Thionyl chloride (25 mL) was added dropwise under 25 cooling (ice bath). The resulting mixture was stirred for 1 hour and the solvents removed in vacuo (rotavap, until p = 20 mm Hg, T + 35°C). The remaining oil was used directly in the synthesis of the ligands, since it was known from the literature that the free picolyl chlorides are somewhat unstable and are highly lachrymatory. To the resultant mixture was added dichloromethane (25 mL) and N-methyl ethylene-1,2- 30 diamine (360 mg, 4.86 mmol). Subsequently NaOH (5 N, aq.) was added dropwise. The reaction was quite vigorous in the beginning, since part of the thionyl chloride was . WO 00/12667 PCT/GB99/02876 still present. The aqueous layer was brought to pH = 10, and additional NaOH (5 N. 4.38 mL) was added. The reaction mixture was stirred until a sample indicated complete conversion (7 days). The reaction mixture was extracted with dichloromethane (3 x 25 mL). The combined organic phases were dried and the solvent 5 removed in vacuo. Purification was enforced by column chromatography (aluminium oxide 90 (activity 11-111 according to Brockmann); triethylamine: ethyl acetate: petroleum ether 40-60 = 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf= 0.9). The compound was eluted using ethyl acetate : triethyl amine = 9:1, yielding N-methyl-N,N,N"-tris(5-methyIpyridin-2- 10 ylmethyl)ethylene-1,2-diamine (L6,685 mg, 1.76 mmol, 36 %) as a slightly yellow oil. 1HNMR: δ 8.31 (s, 3H) 7.43- 7.35 (m,5H), 7.21 (d,j= 7.8,1H), 3.76 (s, 4H), 3.56 (s, 2H), 2.74 - 2.69 (m, 2H), 2.63 - 2.58 (m, 2H), 2.27 (s, 6H), 2.16 (s, 3H); 13CNMR: 5 156.83,156.43,149.23,149.18,136.85,136.81,131.02,122.41, 122.30,63.83,60.38,55.53,52.00,42.76,18.03. 15 Synthesis of N-methyI-N,N,N"-tris(5-ethylpyridin-2-ylmethyl)ethyiene-l,2-diamine (L7). This synthesis is performed analogously to the synthesis for L6. Starting from 2-hydroxymethyl-5-ethyl pyridine (3.00 g, 21.9 mmol), and N-methyl ethylene-1,2-diamine (360 mg, 4.86 mmol), after 7 days N-methyl-N,N,N"-tris(5-ethyIpyridin-2- 20 ylmethyl)ethylene-l ,2-diamine (L7,545 mg, 1.26 mmol, 26 %) was obtained. 1H NMR: δ 8.34 (s, 3H), 7.44 - 7.39 (m, 5H), 7.26 (d, J = 6.6,1H), 3.80 (s, 4H), 3.59 (s, 2H), 2.77 - 2.72 (m, 2H), 2.66 - 2.57 (m, 8H), 2.18 (s, 3H), 123 (t, J= 7.5,9H); 13C NMR: 8 157.14,156.70,148.60,148.53,137.25,135.70,122.59,122.43,63.91, 60.48,55.65,52.11,42.82,25.73,15.36. 25 (jj) Synthesis of metal-ligand complexes: Synthesis of N-methyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-30 diamine iron(II)chloride.PF6([L2 Fe(II)CIIPF6). FeCl24H2O(51.2mg,257 umol) was dissolved in MeOH: H2O = 1:1 (2.5 mL). The solution was heated to 50 °C. WO 00/12667 PCT/GB99/02876 Added was N-methyl-N,N,N;-tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L2,100 mg, 257 umol) in MeOH : H20 = 1:1 (2.0 mL). Subsequently NaPF6 (86.4 mg, 514 umol) in H2O (2.5 mL) was added dropwise. Cooling to room temperature, filtration and drying in vacuo (p = 0.05 mm Hg, T = room temperature)yielded "the 5 complex [L2 Fe(H)CI]PF6 (149 mg, 239 µmol, 93 %) as a yellow solid. 1H NMR (CD3CN, paramagnetic): δ 167.17,142.18,117.01,113.34,104.79,98.62, 70.77,67.04,66.63,58.86,57.56,54.49,51.68,48.56,45.90,27.99,27.36,22.89, 20.57,14.79,12.14,8.41,8.16,7.18,6.32,5.78,5.07,4.29,3.82,3.43.2.91,2.05,1.75, 1.58,0.94,0.53, -0.28, -1.25, -4.82, -18.97, -23.46. 10 Synthesis of N-ethyl-N,N,N"-tris(3-raethylpyridin-2-yImethyl)ethylene-l,2-diamine iron(II)chloride.PF6 ([L3 Fe(II)CI]PF6). This synthesis was performed analogously to the synthesis for [L2 Fe(II)Cl]PF6. Starting from N-ethyl N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L3,104 mg, 257 umol) gave the complex [L3 15 Fe(II)Cl]PF6 (146 mg, 229 umol, 89%) as a yellow solid. 1H NMR (CD3CN, paramagnetic): δ 165.61,147.20,119.23,112.67,92.92,63.14, 57.44,53.20,50.43,47.80,28.59,27.09,22.48,8.55,7.40,3.63,2.95,2.75,2.56,2.26, 1.75,1.58,0.92,0.74,-0.28, -1.68, -2.68, -12.36, -28.75. 20 Synthesis of iV-benzyl-N,N,N",-tris(3-methylpyridin-2-ylniethyl)ethylene-l,2-diamine iron(II)chloride.PF6( ([L4 Fe(II)Cl]PF6). This synthesis was performed analogously to the synthesis for [L2 Fe(II)Cl]PF6. Starting from N-benzyl-N,N,N" tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L4,119.5 mg, 257 umol) gave the complex (172 mg, 229 umol, 95 %) as a yellow solid. 25 1H NMR (CD3CN, paramagnetic): 8 166.33,145.09,119.80,109.45,92.94,57.59, 52.83,47.31,28.40,27.89,16.28,11.05,8.70,8.45,7.69,6.99,6.01,4.12,2.89,2.71, 1.93,1.56, -0.28, -1.68, -2.58, -11.40, -25.32. Example 4 30 This example describes a synmesis of a catalyst of formula (H) wherein:- WO 00/12667 PCT/GB99/02876 (i) Synthesis of the ligand 2,ll-diaza[3,3]-(4-methoxv)(2,6)vvridinoyhane ((4OMe)LNIH2): 10 4-chloro-2.6-pvridvl dimethyl ester (2). A mixture of 4-hvdroxv-2.6-pyridine dicarboxylic acid (12.2 g, 60 mmoles) and PC15 (41.8g, 200 mmoles) in 100 ml of CC14 was refluxed until the evolution of HC1 ceased. Absolute methanol (50ml) was slowly added. After cooling, all the volatile material was removed. The mixture was then poured into 200 ml of water and ice. The diester crystallised immediately and was 15 collected by filtration (70%). 1H NMR (200MHZ, H2O) δ 7.60 (2H,s), 4.05 (6H, s). 4-methoxy-2.6-pyridine dimethanol (4). Metallic sodium (lg, 44 mmoles) was dissolved into 200 ml of dry methanol. 4-chloro-2,6-pyridyl dimethyl ester (9.2 g, 40 mmoles) was then added and the mixture was refluxed for 3 hours to obtain pure 4-methoxy-2,6- 20 pyridyl dimethyl ester. To this solution, at RT, NaBH4 (9.1 g, 240 mmoles) was added in small portions and the mixture was refluxed for 16 hours. Acetone (30 ml) was then added and the solution refluxed for an additional 1 hour. After ail the volatile material was removed, the residue was heated with 60 ml of a saturated NaHCO3/Na2CO3 solution. After dilution with 80 ml of water, the product was continuously extracted WO 00/12667 PCT/GB99/02876 with CHCl3 for 2-3 days. Evaporation of the CHC13 yielded 83 % of 4-methoxy-2,6- pyridine dimethanol. 1HNMR (200MHZ, H20) δ 6.83 (2H,s), 5.30 (2H,s), 4.43 (4Hs), 3.82 (3H, s). 5 4-methoxy-2.6-dichloromethylpridine (5). This synthesis is carried out according literature. N.N"-ditosyl-2.11-diaza[3.3[(4-methoxy)(2,Siuvridinophane. the procedure is similar to that described in the literature. The crude product obtained is practically pure 10 (yield=95%.) 1H-NMR (CDCl3,250 MHz): 7.72 (4H, d, J= 7Hz), 7.4 (1H, t, J= 6Hz), 7,35 (4H, d, J= 7Hz), 7.1 (1H, d, J= 6Hz), 6.57 (2H, s), 4.45 (4H, s), 4.35 (4H, s), 3.65 (3H, s), 2.4 (6H, s). 15 2,1 }-diazaf3.3 ](4-methoxy)(2,6)pyridinophane. The procedure is similar to the one described previously. The crude product obtained is purified by chromatography (alumina, CH2Cl2/MeOH 95:5), yield = 65%. 1H-NMR (CDCl3,250 MHz): 7.15 (1H, t, J= 6Hz), 6.55 (1H, d, J= 6Hz), 6.05 (2H, s), 3.95 (4H, s), 3.87 (4H, s), 3.65 (3H, s). 20 Mass spectrum (EI): M+ = 270 (100%) (ii) Synthesis of the complex rFef4QMeLN,iHV>CMCl: 270 mg of 2,1 l-diaza[3.3]-(4-methoxyX2,6)pyridmophane (1 mmole) were dissolved in 25 15 ml of dry THF. To this solution was added a solution of 270 mg of FeCl3-6H2O (1 mmoles) in 5 ml of MeOH. The resulting mixture is evaporated to dryness and the solid product is dissolved in 10 ml of AcN with a minimum of MeOH. Slow diffusion of THF give 300 mg of brown crystals, yield = 70%. Elemental analysis for C15H18N4Cl3OFe-0,5MeOH (found/theoretical): C=41.5/41.61 H=4.46/4.52 30 N=12.5/12.08 WOOQ/12667 PCT/GB99/02876 IR (KBr pellets, cm"1): 3545,3414,3235,3075,2883,1615,1477,1437,1340,1157, 1049,883,628,338. Example 5: This example describes a synthesis of a catalyst of formula (H) wherein:- 10 R1-R8=H; x-1; y=l; z=l; X=C1, n=2; Y=C1", p=l Synthesis of the complex [Fe(LN4H2)Cl2]CI: 15 240 mg of LN4H2 (1 mmoles) were dissolved in 15 ml of dry THF. To this solution was added a solution of 270 mg of FeCl3-6H2O (1 mmole) in 5 ml of MeOH. The resulting mixture is stirred and gives spontaneously 340 mg of yellow powder, yield = 85%IR (KBr pellets, cm"1): 3445,3031,2851,1629,1062,1473,1427,1335, 1157,1118,1045,936,796,340,318 20 Example 6: This Example describes a synthesis of a catalyst of formula (H) wherein:- WO 00/12667 PCT/GB99/02876 R1=R2=R5-8=H; R3=R4=Me; x=l; y=l; n=2; 2=1; X=F; m=2; Y=PF6; p=l diflouro[N,N"dimethyl-2,11]-diazar3](2.6)DvridinophaneImamanese(IJJ) hexafluorophosphate. 10 (i) Synthesis of the ligand N.N"dimethyl-2.11-diaza[3.31(2.6)pyridinophane: 2.6-dichloromethylpyridine. A mixture of 2,6-dimethanolpyridine (5g, 36 ramoles) and 75 ml of SOl2 was refluxed for 4 hours. The mixture was concentrated (half volume). Toluene was added (50 ml). The solid formed after cooling was then filtered and 15 dissolved in water and the solution neutralised with NaHCO3. The solid obtained is filtered and dried (65%). 1H NMR (200MHZ, CDCl3) δ 7.8 (lH,t, J=7Hz), 7.45 (2H,d, J=7Hz),4.7(4H,s). Sodium v-toluenesulphonamidure. To a mixture of Na° in dry EtOH (0.7 g, 29 mmolcs) 20 was added/7-toluenesulphonamide (5 g, 29 mmoles) and the solution was refluxed for 2 hours. After cooling, the solid obtained was filtered, washed with EtOH and dried (quantitative yield). N.N"-ditosyl-2, J 1-diaza[3.3](2.6)pyidinophane. To a solution of sodium p- 25 toluenesulphonamidure (1.93 g, 10 mmoles) in 200 ml of dry DMF at 80°C was slowly added 2,6-dichloromethylpyridine (1.76 g, 10 mmoles). After 1 hour a new portion of sodium p-toluenesulphonamidure was added (1.93 g) and the final mixture stirred at WO 00/12667 PCT/GB99/02876 80°C for an addition 4 hours. The solution was then evaporated to dryness. The solid obtained was washed with water and then with EtOH and finally crystallised in an CHCl3/MeOH mixture. The solid obtained is filtered and dried. The yield of (15) was 55 %. 1H NMR (200MHz, CDC13) δ 7.78 (4H,d, J=6Hz), 7,45 (6H,m), 7,15 ( 4Hd, 5 J=6Hz), 4.4 (8H, s), 2.4 (6H,s) 2.11-diaza[33](2.6)pvridinonhane. A mixture of N,N"-ditosyl-2.11-diaza[3.3] (2,6)pyridinophane (1.53 g, 2.8 mmoles) and 14 ml of H2SO4 90 % was heated at 110°C for 2 hours. The solution, cooled and diluted with 14 ml of water, was then carefully 10 poured into a saturated NaOH solution. The solid formed is extracted with chloroform. The organic layer is evaporated to dryness to yield 85 % of 2,ll-diaza[3.3](2,6)pyridinophane. 1H NMR (200MHz, CDCl3) δ 7.1 (2H,t, J=7Hz), 6.5 (4H,d, J=7 Hz), 3.9 (8H, s). 15 N,N"-dimethyl-2,11-diaza[3.3](2.6)pyidinophane. A mixture of 2,ll-diaza[3.3] (2,6)pyridinophane (0.57 g, 2.4 mmoles), 120 ml of formic acid and 32 ml of formaldehyde (32% in water) was refluxed for 24 hours. Concentrated HC1 (10 ml) were added and the solution evaporated to dryness. The solid was dissolved in water and basified with NaOH 5M, and the resulting solution was extracted with CHC13. The solid 20 obtained was purified by chromatography on alox (CH2Cl2+ t% MeOH) to yield 51 % of N,N-dimethyl-2,11-diaza[3.3](2,6)pyridinophane. 1H NMR (200MHz, CDCl3) 8 7.15 (2H,t, J=7Hz), 6.8 (4H,d, J=7 Hz), 3.9 (8H, s), 2.73 (6H,s). (ii) Synthesis of the complex; MnF3 (41.8 mg, 373 mmoles) was dissolved in 5 ml of MeOH, and N,N"-dimethyl-2,11- diaza[3.3](2,6)pyridinophane (0.1 g, 373 mmoles) was added with 5 ml of THF. After 30 minutes of stirring at RT, 4 ml of THF saturated in NBu4PF6 were added, and the solution left without stirring until the crystallisation was finished. The product was 30 collected by filtration to yield 80% of complex. Elemental analysis (found, theoretical): %C (38.35, 37.94), %N (11.32, 11.1), %H (3.75, 3.95). IR (KBr pellet, cm-1): 3086, WO 00/12667 PCT/GB99/02876 2965,2930,2821,1607, 1478,1444,1425,1174,1034. 1019, 844, 796, 603r 574. 555. UV-Vis (CH3CN, X in nm, E): 500, 110; 850, 30; (CH3CN/H20:1/1, X in nm, e): 465, 168; 850,30. 5 Example 7: Bleaching of tomato-oil stained cloths without and with addition of [Fe(MeN4Py)(CH3CN)](ClO4)2, immediately after the wash (t=0) and after 24 h storage (t=l day). 10 In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/1 LAS (linear alkylbenzene sulphonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/1 LAS, tomato-soya oil stained cloths (6x6 cm) were added and stirred for 30 minutes at 30 °C. In a second series of experiments, the same tests were done in the presence of 10 µM [Fe(MeN4Py)CH3CN)](C1O4)2. referred to in the table below as 15 Fe(MeN4Py). After the wash, the cloths were dried in a tumble drier and the reflectance was measured with a Minolta 3700d spectrophotometer at 460 nm. The difference in reflectance before and after the wash is defined as AR460 value. 20 The cloths were measured immediately after the wash (t=0), and after 24 h storage in a dark room under ambient conditions (t=ld). The results obtained are listed in the table below: WO 00/12667 PCT/GB99/02876 Example 8: Bleaching of tomato-oil stained cloths without and with addition of various metal catalysts measured immediately after drying. 5 In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/l LAS (linear alkylbenzene sulphonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/l LAS, tomato-soya oil stained cloths were added and kept in contact with the solution under agitation for 30 minutes at 30 °C. In comparative experiments, the same experiments were done by addition of 5 µM of dinuclear or 10 10 uM mononuclear complex, referred to in the table below. After the wash, the cloths were rinsed with water and subsequently dried at 30 °C and the change in colour was measured immediately after drying with a Linotype-Hell scanner (ex Linotype). The change in colour (including bleaching) is expressed as the 15 AE value. The measured colour difTerence (AE) between the washed cloth and the unwashed cloth is defined as follows: ΔE = [ΔL)2 +(Δa)2 +(Δb)2 ]1/2 20 wherein AL is a measure for the difference in darkness between the washed and unwashed test cloth; Aa and Ab are measures for the difference in redness and yellowness respectively between both cloths. With regard to this colour measurement technique, reference is made to Commission International de rEclairage (CIE); Recommendation on Uniform Colour Spaces, colour difference equations, psychometric 25 colour termsL supplement no 2 to CIE Publication, no 15, Colormetry, Bureau Central de la CIE, Paris 1978. The following complexes were used: 30 i) [Mn2(l,4,7-trimethyl-l,4,7-triazacyclononane)2(µ0)3](PF6)2(l) Synthesized according to EP-B-458397; WO 00/12667 PCT/GB99/02876 ii) [Mn(LN4Me2)] (=difluoro[N,N,dimethyl-2,ll-diaza[3.3](2,6)pyridinophane] manganese(III)hexafluorophosphate) (2) Synthesized as described previously; 5 iii) [Fe(OMe)LN4H2)Cl2] (=Fe(2,l l-diaza[3.3]-(4-methoxy(2,6)pyridinophane)Cl2 (3) Synthesised as described previously; 10 iv) C12-CoCo(4) Synthesised according to EP-A-408131; v) Me2CoCo(5) Synthesised according to EP-A-408131; 15 vi) [Fe(tpen)](C104)2(6) Syfithesised according to WO-A-9748787; vii) [Fe(N,N,N,-tris(pyridin-2ylmethyl)-N-methyl-l ,2-€thylenediamine)Cl](PF6)2 (7) 20 Synthesised according to I. Bernal, el al, J. Chem. Soc, Dalton Trans. 22, 3667 (1995); viii) [Fe2(N,N,N"-tetrakis(benzimidazol-2-ylmethyl)-propan-2-ol-l 3-diamine)(µ- OH)NO3)2](NO3)2(8) 25 Synthesised according to Brennan, et al, Inorg. Chem., 30,1937 (1991); ix) [Mn2(tpen)µ-O)2(µ-OAc)](ClO4)2(9) Synthesised according to Toftlund, R; Markiewicz, A.; Murray, K.S.; Acta Chem. Scamd, 44, 443 (1990); WO 00/12667 PCT/GB99/02876 x) [Mn(N.NN"-tris(pyridin-2-ylmethy)N"-methyl-l,2-ethylenediamine)Cl](PF6) (10) Synthesised as follows: To a solution of manganese chloride tetrahydrate m tetrahydrofuran xi) [Mn2(N,N"-bis(pyridin-2-ylmethy)-l,2-ethylenediamine)2(µ-O)2](ClO4)3(11) Synthesised according to Glerup, J.; Goodson, P. A.: Hazett, A.; Hazell, R.: 15 Hodgson, D. J.; McKenzie, C. J.; Michelsen, K.; Rychlewska, U.; Toftlund, H. Inorg. Chem. (1994), 33(18), 4105-11; xii) [Mn(N,N"-bis(pyridin-2-ylmethyl)N,N,-dimethyl-1,2-ethyIenediamine)2Cl2] (12) Synthesised as follows: 20 Triethylamine (0.405g, 4 mmol) was a solution of salt of the ligand bispicen(NMe) (0.416g, 1 mmol) in tetrahydrofuran anhydrous (10 mL) (ref ligand: C. Li, et al, J. Chem. Soc, Dalton Trans. (1991), 1909-14). The mixture was stirred at room temperature for 30 minutes. A few drops of methanol were added. The mixture was filtered. Manganese chloride (0.198g, 1 mmol) dissolved in THF (1 mL) was added 25 to the mixture to give, after a stirring of 30 minutes, a white precipitate. The solution was filtered, the filtrate was washed twice with dry ether and dried under vacuum. This gave 0.093g of complex (23% yield). xiii) [Mn2(N,N,N"N"-tetrakis(pyridin-2-ylmethyl)-propan-1,3-diamine)(µ,-O)(µ-30 OAc)2](C1O4)2(13) Synthesised as follows: WO 00/12667 PCT/GB99/02876 58 To a stirred solution of 6.56 g 2-chloro-methylpyridine (40 mmol) and 0.75 ml 1,3-propanediamine (9 mmol) in 40 ml water, is added slowly at 70°C over a period of 10 minutes, 8 ml 10M NaOH-solution, The colour of the reaction turned from yellow to deep red. The reaction was stirred for an additional 30 minutest 70°C? after which the 5 reaction was cooled to room temperature. The reaction mixture was extracted with dichloromethane (totally 200 ml), after which the red organic layer was dried over MgSC>4, filtered and evaporated under reduced pressure, to yield 4.51 g of a red/brown oil. After scratching the bottom with a spatula the residue turned solid, trying to purify the crude product by washing it with water the product became messy, so immediately 10 the purification was stopped and dried with ether. A sample was taken to analyse the product by NMR, while the rest was immediately reacted with Mn(OAc)a (see complexation). !H-NMR (400MHz) (CDC13); d (ppm): 1.65 (q-5, propane-A, 2H), 2.40 (t, propane-B, 4H), 3.60 (s, N-CH2-pyr, 8H), 6.95 (t, pyr-H4, 4H), 7.30 (d, pyr-H3, 4H), 7.45 (t, pyr- 15 H5,4H), 8.35 (d, pyr-H6,4H). To a stirred solution of 4.51 g TPTN (0.0103 mol) in 40 ml methanol is added at room tenipemture (22°C) 2.76 g Mn(OAc)3 (0.0103 mol) . The colour of the reaction turned from orange to dark brown, after the addition the mixture was stirred for 30 minutes at room temperature and filtered. To the filtrate was added at room temperature 20 1.44 g NaC104 (0.0103 mmol) arid the reaction mixture was stirred for another hour, filtered and nitrogen dried, yielding 0.73 g bright brown crystals (8%). "H-NMR (400MHz) (CD3CN); d (ppm): -42.66 (s), -15.43 (s), -4.8 (s, br.), 0-10 (m, br.), 13.8r(s), 45.82 (s), 49.28 (s), 60 (s, br,), 79 (s, br.), 96 (s, br.) W (cm-1): 3426, 1608 (C=C), 1563 (C=N), 1487 , 1430 (C-H), 1090 (C104), 1030, 25 767,623. UV/Vis (K nm(s, hnol"W): 260 (2.4 xlO4), 290 (sh), 370 (sh), 490 (5.1 xlO2), 530 (sh; 3.4 xlO2); 567 (sh), 715 (1.4 x 102). Mass spectrum: (ESP+) m/z 782 [TPTN Mn(II)Mn(III) (u-OH) (u-OAc)2 (C104) ESR (CH3CN): The complex is ESR silent supporting the presence of a Mn(in)Mn(IH) 30 species. WO 00/12667 PCT/GB99/02876 Elemental analysis: found (expected for Mn2C31H38N6O14C12 (MW=899): C 41.14 (41.4), H 4.1 (4.2), N 9.23 (9.34), 0 24.8 (24.9), CI 7.72 (7.9), Mn 12.1 (12.2). xiv) [Mn2(tpa)2(µ-O)2](PF6)3 (14) 5 Synthesised according to D.K. Towle, C.A. Botsford, DJ. Hodgson, ICA, 141, 167(1988); xv) [Fe(N4PyXCH3CN)](C1O4)2(15) Synthesised according to WO-A-9534628; 0 xvi) [Fe(MeN4PyXCH3CN)](C1O4)2 (16) Synthesised according to EP-A-0909809. 15 Results: BL: Reference: no catalyst added, only buffer with and without LAS Compound 16 with 10 mM hydrogen peroxide Table: bleach activity on Tomato Oil stains expressed in AE values obtained for various metal complexes. WE CLAIM: 1. A process for the manufacture of a bleaching composition adapted to bleach a substrate by the atmospheric oxygen comprising the step of providing a bleach catalysing complex obtained of an organic substrate of formula L and a transition metal such that the bleaching composition obtained thereof upon addition to an aqueous medium provides an aqueous bleaching medium substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system, wherein L represents a ligand of the general formula (BI): wherein g represents zero or an integer from 1 to 6; r represents an integer from 1 to 6; s represents zero or an integer from 1 to 6; Zl and Z2 independently represent a heteroatom or a heterocyclic or heteroaromatic ring, Zl and/or Z2 being optionally substituted by one or more functional groups E as defined below; Ql and Q2 independently represent a group of the formula: wherein 10>d+e+f>l; d=0-9; e=0-9; fM)-9; each Yl is independently selected from -0-, -S-, -SO-, -SO2-, -(G1)N-, -(G1)(G2)N-(wherein G1 and G2 are as defined below), -C(O)-, arylene, alkylene, heteroarylene, -P-and -P(O)-; if s>l, each -[-Zl(Rl)-(Ql)r-]- group is independently defined; Rl, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen; E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from hydroxy, mono- or polycarboxylate derivatives, aryl, heteroaryl, sulphonate, thiol (-RSH), thioethers (-R-S-R), disulphides (-RSSR), dithiolenes, mono- or polyphosphonates, mono- or polyphosphates, electron donating groups and electron withdrawing groups, and groups of formulae (G1)(G2)N-, (G )(G ) (G3)N-, (G1)(G2)N-C(O)-, G3O- and G3C(O)-, wherein each of G1, G2 and G3 is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoing)); or one of R1-R9 is a bridging group bound to another moiety of the same general formula; Tl and T2 independently represent groups R4 and R5, wherein R4 and R5 are as defined for R1-R9, and if g=0 and s>0, Rl together with R4, and/or R2 together with R5, may optionally independently represent =CH-R10, wherein R10 is as defined for Rl-R9, or Tl and T2 may together (-T2-T1-) represent a covalent bond linkage when s>l and g>0; if Zl and/or Z2 represent N and Tl and T2 together represent a single bond linkage and Rl and/or R2 are absent, Ql and/or Q2 may independently represent a group of the formula: =CH-[-Yl-]e-CH=, optionally any two or more of Rl, R2, R6, R7, R8, R9 independently are linked together by a covaient bond; if Zl and/or Z2 represents O, then Rl and/or R2 do not exist; if Zl and/or Z2 represents S, N, P, B or Si then Rl and/or R2 may be absent; if Zl and/or Z2 represents a heteroatom substituted by a functional group E then Rl and/or R2 and/or R4 and/or R5 may be absent. 2. A method as claimed in claim 1, wherein Zl and Z2 independently represent an optionally substituted heteroatom selected from N, P, O, S, B and Si or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrrolidines, pyrazine, pyramidine, pyrazole, pyrrole, imidazole, benzimidazole, quinoleine, isoquinoline, carbazole, indole, isoindole, furane, thiophene, oxazole and thiazole. 3. A method as claimed in anyone of claims 1 or 2, wherein R1-R9 are independently selected from -H, hydroxy-C0-C20-alkyl, halo-C0-C20-alkyl, nitroso, formyl-C0-C20-alkyl, carboxyl-.C0-C20-alkyl and esters and salts thereof, carbamoyl-Co-C20-alkyl, sulpho-C0-C20-alkyl and esters and salts thereof, sulphamoyl-C0-C20-alkyl, amino-C0-C20-alkyl, aryl-C0-C20-alkyl, heteroaryl-C0-C20-alkyl, C0-C20-alkyl, alkoxy-C0-C8-alkyl, carbonyl-C0-C6-alkoxy, and aryl-C0-C6 alkyl and Co-C2o-alkylamide; or one of R1-R9 is a bridging group -Cn(Rll)(R12)-(D)p-Cm(Rll)(R12)- bound to another moiety of the same general formula, wherein p is zero or one, D is selected from a heteroatom or a heteroatom-containing group, or is part of an aromatic or saturated homonuclear and heteronuclear ring, n" is an integer from 1 to 4, m" is an integer from 1 to 4, with the proviso that n"+m" 4. A method as claimed in any one of claims 1 to 2, wherein Tl and T2 together form a single bond linkage and s>l, as claimed in claimgeneral formula (BII): wherein Z3 independently represents a group as defined for Zl or Z2; R3 independently represents a group as defined for R1-R9; Q3 independently represents a group as defined for Ql, Q2; h represents zero or an integer from 1 to 6; and s"=s-l. 5. A method as claimed in claim 4, wherein in general formula (BII) used s"=l, 2 or 3; r=g=h=l; d=2 or 3; e=f=0; R6=R7=H. 6. A method as claimed in claim 5, wherein the ligand used has a general formula selected from: 7. A method as claimed in claim 6, wherein the ligand used has a general formula selected from: 8. A method as claimed in claim 7, wherein Rl, R2, R3 and R4 are independently selected from -H, alkyl, heteroaryl, or represents a bridging group bound to another moiety of the same general formula with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge. 9. A method as claimed in claim 8, wherein Rl, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula with the bridging group being alkylene or hydroxy-alkylene. 10. A method as claimed in any of claims 5 to 9, wherein in the complex [MaLkXn]Ym used: M= Mn(II)-(IV), Cu(I)-(III), Fe(II)-(III), Co(II)-(HI); X= CH3CN, OH2, C1, Br, OCN", N3-, SCN", Off , O2-, PO43", C6H5BO22-, RCOO"; Y= C104 BPV, Br", C1 , [FeCl4] PF6", NO3" a= 1, 2, 3, 4; n= 0, 1, 2, 3, 4, 5, 6,7, 8, 9; m= 1, 2, 3, 4; and k= 1, 2, 4. 11. A method as claimed in claim 4, wherein in general formula (BII) used s"=2; r=g=h=l; d=f=0; e=l; and each Yl is independently alkylene or heteroarylene. 12. A method as claimed in claim 11, wherein the ligand used has the general formula: wherein A1, A2, A3, A4 are independently selected from C1-9-alkylene or heteroarylene groups; and N1 and N2 independently represent a hetero atom or a heteroarylene group. 13. A method as claimed in claim 12, wherein N1 represents an aliphatic nitrogen; N2 represents a heteroarylene group; Rl, R2, R3, R4 each independently represent -H, alkyl, aryl or heteroaryl; and Ai, A2, A3, A4 each represent -CH2-. 14. A method as claimed in claim 13, wherein the ligand used has the general formula: wherein Rl, R2 each independently represent -H, alkyl, aryl or heteroaryl. 15. A method as claimed in anyone of claims 11 to 14, wherein in the complex [MaLkXn] Ym used : M= Fe(II)-(III), Mn(II)-(IV), Cu(II), Co(II)-(III); X= CH3CN, 0H2, C1", Br", OCN", N3 SCN, OH" , O2-, P043 C6H5BO22-, RCOO"; Y= C1O4, BPh4 Br", CI", [FeCl4] PF6 NO3"; a= 1, 2, 3, 4; n= 0, 1, 2, 3, 4, 5, 6,7, 8, 9; m= 1, 2, 3, 4; and k= 1, 2, 4. 16. A method as claimed in claim 14, wherein in general formula (BII) used s"=2 and r=g=h=l, as claimed in the general formula: 17. A method as claimed in claim 16, wherein Zl=Z2=Z3=Z4=a heteroaromatic ring; e=f=0; d=l; and R7 is absent. 18. A method as claimed in claim 16, wherein Z1-Z4 each represent N; R1-R4 are absent; both Ql and Q3 represent =CH—[—Yl— ]e—CH= ; and both Q2 and Q4 represent -CH2-[-Yl-]m-CH2-. 19. A method as claimed in claim 18, wherein the ligand used has the general formula: wherein A represents optionally substituted alkylene optionally interrupted by a heteroatom; and n is zero or an integer from 1 to 5. 20. A method as claimed in claim 19, wherein R1-R6 represent hydrogen, n=l and A= -CH2-, -CHOH-, -CH2N(R)CH2- or -CH2CH2N(R)CH2CH2- wherein R represents hydrogen or alkyl. 21. A method as claimed in claim 20, wherein A= -CH2-, -CHOH- or -CH2CH2NHCH2CH2-. 22. A method as claimed in anyone of claims 13 to 21, wherein in the complex [MaLkXn]Ymused : M= Mn(II)-(IV), Co(II)-(III), Fe(II)-(III); X= CH3CN, OH2, C1", Br", OCN", N3", SCN", OFT , O2", PO43- C6H5BO22 RCOO"; Y= C1O4", BPh4", Br -, C1", [FeCl4] PF6", NO3" a= 1, 2, 3, 4; n= 0,1, 2, 3, 4, 5, 6,7, 8, 9; m= 1, 2, 3, 4; and k= 1, 2, 4. 23. A method as claimed in anyone of claims 1 to 3, wherein Tl and T2 independently represent groups R4, R5 as defined for R1-R9, as claimed in the general formula (BIII): 24. A method as claimed in claim 23, wherein in general formula (BIII) used, s=l; r=l; g=0; d=f=l; e=l-4; Yl= -CH2-; and Rl together with R4, and/or R2 together with R5, independently represent =GH-R10, wherein R10 is as defined for R1-R9. 25. A method as claimed in claim 24, wherein R2 together with R5 represents =CH- R10. 26. A method as claimed in claim 24 or claim 25, wherein the ligand used is selected from: 27. A method as claimed in claim 26, wherein the ligand used is selected from: wherein Rland R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, heteroaryl-C0-C20-alkyls, alkylaryl, aminoalkyl, alkoxy. 28. A method as claimed in claim 27, wherein Rl and R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-Co-C2-alkyls. 29. A method as claimed in anyone of claims 37 to 41 wherein in the complex [MaLkXn]Ymused: M= Mn(II)-(IV), Co(II)-(III), Fe(II)-(III); X= CH3CN, OH2, C1", Br", OCN", N3", SCN", OH , O2", PO43", C6H5BO22", RCOCr; Y= C1O4", BPh4", Br", C1", [FeCl4]", PF6 NO3"; a= 1, 2, 3, 4; n= 0,1,2,3,4,5,6,7,8,9; m= 1, 2, 3, 4; and k= 1, 2, 4. 30. A method as claimed in claim 23, wherein in general formula (Bill) used, s=l; r=l; g=0; d=f=l; e=l-4; Yl= -C(R")(R"X wherein R" and R" are independently as denned for R1-R9. 31. A method as claimed in claim 30, wherein the ligand used has the general formula: 32. A method as claimed in claim 31, wherein Rl, R2, R3, R4, R5 are -H or C0-C20-alkyl, n=0 or 1, R6 is -H, alkyl, -OH or -SH, and R7, R8, R9, R10 are each independently selected from -H, Co-C20-a!kyl, heteroaryl-C0-C20-alkyl, alkoxy-C0-C8-alkyl and amino- CcrC20-alkyl. 33. A method as claimed in anyone of claims 30 to 32, wherein in the complex [MaLkXn]Ym used: M= Mn(II)-(IV), Fe(II)-(III), Cu(II), Co(H)-(III); X= CH3CN, OH2, C1, Br", OCN", N3, SCN Off , O2- , PO4", C6H5BO2 , RCOO 3 Y= C1O4", BPh4", Br", C1", [FeCl4]-, PF6", NO3"; a= 1, 2, 3, 4; n= 0,1,2,3,4; m= 0, 1, 2, 3, 4, 5, 6, 7, 8; and k= 1, 2, 3, 4. 34. A method as claimed in claim 23, wherein in general formula (BIII) used, s=0; g=l;d=e=0;f=l-4. 35. A method as claimed in claim 34, wherein the ligand used has the general formula: wherein Rl, R2, R3 are as defined for R2, R4, R5. 36. A method as claimed in claim 35, with the proviso that none of Rl to R3 represents hydrogen. 37. A method as claimed in claim 35 or claim 36, wherein the ligand used has the general formula: 38. A method as claimed in anyone of claims 34 to 37, wherein in the complex [MaLkXn] Ym used : M= Mn(II)-(IV), Fe(II)-(III), Cu(II), Co(II)-(III); X= CH3CN, OH2, CI", Br", OCN, N3 SCN, OH" , O2 PO43", C6H5BO22-, RCOO"; Y= C1O4 BPh4", Br", C1", [FeCl4]", PF6 NO3"; a= 1, 2, 3, 4; n= 0,1,2,3,4; m= 0, 1, 2, 3, 4, 5, 6, 7, 8; and k= 1, 2, 3, 4. 39. A method as claimed in anyone of claims 1 to 3, wherein L represents a pentadentate ligand of the general formula (B): wherein each R1, R2 independently represents -R4-R5, R3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R4-R5, each R4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and each R5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl. 40. A method as claimed in claim 39, with the proviso that R3 does not represent hydrogen. 41. A method as claimed in anyone of claims 1 to 3, wherein L represents a pentadentate or hexadentate ligand of the general formula (C): R1R1N-W-NR1R2 wherein each R1 independently represents -R3-V, in which R3 represents optionally substituted alkylene, alkenylene, oxyalkylene, arninoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl; W represents an optionally substituted alkylene bridging group selected from -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2-, and -CH2-C10H6-CH2-; and R2 represents a group selected from R1, and alkyl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R4 )3, wherein R4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether and alkenyl ether. 42. A method as claimed in anyone of claims 1 to 3, wherein L represents a macrocyclic ligand of formula (E): wherein Z1 and Z2 are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring structure being substituted by one or more substituents; Yl and Y2 are independently selected from C, N, O, Si, P and S atoms; A1 and A2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl) being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulphonate, phosphate, electron donating groups and electron withdrawing groups, and groups of formulae (G1)(G2)N-, G3OC(O)-, G3O-and G3C(O)-, wherein each of G1, G2 and G3 is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups (in addition to any amongst the foregoing); i and j are selected from 0, 1 and 2 to complete the valency of the groups Y1 and each of Q -Q is independently selected from groups of formula wherein 10>a+b+c+d>2; each Y3 is independently selected from -0-, -S-, -SO-, -S02-, -(G1)(G2)N-, -(G!)N- (wherein G1 and G2 are as hereinbefore defined), -C(O)-, aryl, heteroaryl, -P- and -P(O)-; each of A3-A6 is independently selected from the groups hereinbefore defined for A1 and A2; and wherein any two or more of A1-A6 together form a bridging group, provided that if A1 and A2 are linked without simultaneous Unking also to any of A3-A6, then the bridging group linking A1 and A2 must contain at least one carbonyl group. 43. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a pH value in the range from pH 6 to 11. 44. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a pH value in the range from pH 8 to 10. 45. A method as claimed in any preceding claims wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a medium substantially devoid of a transition metal sequestrant. 46. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a medium further comprising a surfactant. 47. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a medium comprising a builder. 48. A method as claimed in any preceding claims, wherein the organic substance comprises a preformed complex of a ligand and a transition metal. 49. A method as claimed in any one of claims 1 to 47, wherein the organic substance used comprises a free ligand that complexes with a transition metal present in the water. Dated this 1st day of March 2001 ANJAN SEN Of S. MAJUMDAR & CO. Applicants" Agent

Full Text

FORM -2
THE PATENTS ACT, 1970
(39 OF 1970)
COMPLETE SPECIFICATION
(See Section 10; rule 13)
1. TITLE OF INVENTION
COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE
2. HINDUSTAN LEVER LIMITED, a company incorporated under the Indian Companies Act, 1913, and having its registered office at Hindustan Lever House, 165/166 Backbay Reclamation, Mumbai -400 020, Maharashtra, India

The following specification particularly describes the nature of the invention and the manner in which it is to be performed.

COMPOSITION AND METHOD FOR BLEACHING A SUBSTRATE
This invention relates to compositions and methods for catajytically bleaching substrates with atmospheric oxygen.
Peroxygen bleaches are well known for their ability to remove stains from substrates. Traditionally, the substrate is subjected to hydrogen peroxide, or to substances which can generate hydroperoxyl radicals, such as inorganic or organic peroxides. Generally, these systems must be activated. One method of activation is to employ wash temperatures of 60°C or higher. However, these high temperatures often lead to inefficient cleaning, and can also cause premature damage to the substrate.
A preferred approach to generating hydroperoxyl bleach radicals is the use of inorganic peroxides coupled with organic precursor compounds. These systems are employed for many commercial laundry powders. For example, various European systems are based on tetraacetyl ethylenediamine (TAED) as the organic precursor coupled with sodium perborate or sodium percarbonate, whereas in the United States laundry bleach products are typically based on sodium nonanoyloxybenzenesulphonate (SNOBS) as the organic precursor coupled with sodium perborate.
Precursor systems are generally effective but still exhibit several disadvantages. For example,oganic precursors are moderately sophisticated molecules requiring multi-step manufacturing processes resulting in high capital costs. Also, precursor systems have large formulation space requirements so that a significant proportion of a laundry powder must be devoted to the bleach components, leaving less room for other active ingredients and complicating the development of concentrated powders. Moreover, precursor systems do not bleach very efficiently in countries where consumers have

WO 00/12667 PCT/GB99/02876

wash habits entailing low dosage, short wash times, cold temperatures and low wash liquor to substrate ratios.
Alternatively, or additionally, hydrogen peroxide and peroxy systems, can be activated 5 by bleach catalysts, such as by complexes of iron and the ligand N4Py (i. e. N. N-bis(pyridin-2-yl-methyl)-bis(pyridin-2-yl)methylamine) disclosed in W095/34628. or the ligand Tpen (i.e. N, N, N\ N"-tetra(pyridin-2-yl-methyl)ethylenediamine) disclosed in W097/48787. According to these publications, molecular oxygen may be used as the oxidant as an alternative to peroxide generating systems. However, no role in catalysing 10 bleaching by atmospheric oxygen in an aqueous medium is reported.
It has long been thought desirable to be able to use atmospheric oxygen (air) as the source for a bleaching species, as this would avoid the need for costly hydroperoxyl generating systems. Unfortunately, air as such is kinetically inert towards bleaching
15 substrates and exhibits no bleaching ability. Recently some progress has been made in this area. For example, WO 97/38074 reports the use of air for oxidising stains on fabrics" by bubbling air through an aqueous solution containing an aldehyde and a radical initiator. A broad range of aliphatic, aromatic and heterocyclic aldehydes is reported to be useful, particularly para-substituted aldehydes such as 4-methyl-, 4-ethyl- and 4-
20 isopropyl benzaldehyde, whereas the range of initiators disclosed includes N-
hydroxysuccinimide, various peroxides and transition metal coordination complexes.
However, although this system employs molecular oxygen from the air, the aldehyde component and radical initiators such as peroxides are consumed during the bleaching 25 process. These components must therefore be included in the composition in relatively high amounts so as not to become depleted before completion of the bleaching process in the wash cycle. Moreover, the spent components represent a waste of resources as they can no longer participate in the bleaching process.
30 Accordingly, it would be desirable to be able to provide a bleaching system based on atmospheric oxygen or air that does not rely primarily on hydrogen peroxide or a

WO 00/12667 PCT/GB99/02876
hydroperoxyl generating system, and that does not require the presence of organic components such as aldehydes that are consumed in the process. Moreover, it would be desirable to provide such a bleaching system that is effective in aqueous medium.
5 We have surprisingly found that the long held wish to use atmospheric oxygen or air for bleaching substrates can be fulfilled without the attendant disadvantages referred to above. This has now been achieved by means of an organic substance that catalyses bleaching of the substrate by atmospheric oxygen, using the composition and method in accordance with the present invention.
10
Accordingly, in a first aspect, the present invention provides a bleaching composition comprising, in an aqueous medium, atmospheric oxygen and an organic substance which forms a complex with a transition metal, the complex catalysing bleaching of a substrate by the atmospheric oxygen, wherein the aqueous medium is substantially
15 devoid of peroxygen bleach or a peroxy-based or -generating bleach system. The medium is therefore preferably insensitive or stable to catalase, which acts on peroxy species,
In a second aspect, the present invention provides a method of bleaching a substrate 20 comprising applying to the substrate, in an aqueous medium, an organic substance
which forms a complex with a transition metal, the complex catalysing bleaching of the substrate by atmospheric oxygen.
Furthermore, in a third aspect, the present invention provides the use of an organic 25 substance which forms a complex with a transition metal as a catalytic bleaching agent for a substrate in an aqueous medium substantially devoid of peroxygen bleach or a peroxy-based or -generating bleach system, the complex catalysing bleaching of the substrate by the atmospheric oxygen.
30 Advantageously, the method according to the present invention permits all or the
majority of the bleaching species in the medium (on an equivalent weight basis) to be

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derived from atmospheric oxygen. Thus, the medium can be made wholly or substantially devoid of peroxygen bleach or a peroxy-based or generating bleach system. Furthermore, the organic substance is a catalyst for the bleaching process and, as such, is not consumed but can continue to participate in the bleaching process. The 5 catalytically activated bleaching system of the type in accordance with the present invention, which is based on atmospheric oxygen, is therefore both cost-effective and environmentally friendly.
Moreover, the bleaching system is operable under unfavourable wash conditions which 10 include low temperatures, short contact times and low dosage requirements.
Furthermore, the method is effective in an aqueous medium and is therefore particularly applicable to bleaching of laundry fabrics. Therefore, whilst the composition and method according to the present invention may be used for bleaching any suitable 15 substrate, the preferred substrate is a laundry fabric.
The bleaching method may be carried out by simply leaving the substrate in contact with the medium for a sufficient period of time. Preferably, however, the aqueous medium on or containing the substrate is agitated.
20
The organic substance may comprise a preformed complex of a ligand and a transition metal. Alternatively, the organic substance may comprise a free ligand that complexes with a transition metal already present in the water or that complexes with a transition metal present in the substrate. The organic substance may also be included in the form
25 of a composition of a free ligand or a transition metal-substitutable metal-ligand
complex, and a source of transition metal, whereby the complex is formed in situ in the medium. "
The organic substance forms a complex with one or more transition metals, in the latter 30 case for example as a dinuclear complex. Suitable transition metals include for
example: manganese in oxidation states II-V, iron I-IV, copper I-III, cobalt I-III, nickel

WO 00/12667 PCT/GB99/02876
I-III, chromium II-VII, silver I-II. titanium II-IV. tungsten IV-VI. palladium II, ruthenium II-V, vanadium II-V and molybdenum II-VL
In a preferred embodiment, the organic substance forms a complex of the general 5 formula (Al):

in which: 10
15 L represents a ligand as herein defined, or its protonated or deprotonated
analogue;
"X represents a coordinating species selected from any mono, bi or tri charged
anions and any neutral molecules able to coordinate the metal in a mono, bi or tridentate
manner, preferably selected from 20
and more preferably selected from

25 Y represents any non-coordinated counter ion, preferably selected from

and BF4", and more preferably selected from 30

WO 00/12667 PCT/GB99/02876

R, R", R", R"" independently represent a group selected from hydrogen, hydroxyl. -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaiyl or carbonyl derivative group), -OAr. alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaiyl and carbonyl derivative groups, each of R, Ar, alkyl. alkenyl, cycloalkyl, 5 heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen, wherein E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups, and preferably R. R\ 10 R", R" represent hydrogen, optionally substituted alkyl or optionally substituted aryl, more preferably hydrogen or optionally substituted phenyl, naphthyl or C1-4-alkyl;
a represents an integer from 1 to 10, preferably from 1 to 4;
k represents an integer from 1 to 10;
n represents zero or an integer from 1 to 10, preferably from 1 to 4;
IS m represents zero or an integer from 1 to 20, preferably from 1 to 8.
Preferably*, the ligand L is of the general formula (BI):
Tl-[-Zl-(Ql)r-]s-22-(Q2)g-T2
20 Rl R2
wherein
g represents zero or an integer from 1 to 6;
r represents an integer from 1 to 6;
25 s represents zero or an integer from 1 to 6;
Zl and Z2 independently represent a heteroatom or a heterocyclic or heteroaromatic ring, Zl and/or Z2 being optionally substituted by one or more functional groups E as defined below; 30
Ql and Q2 independently represent a group of the formula:

WO 00/12667 PCT/GB99/02876

5
wherein
10>d+e+f>l; d=0-9; e=0-9; f=0-9;
each Yl is independently selected from -0-, -S-, -SO-, -SO2-, -(G1)N-, -(G1)(G2)N- (wherein G1 and G2 are as defined below), -C(O)_, arylene, alkylene, 10 heteroarylene, -P- and -P(O)-;
if s>l, each -[-Zl(Rl)-(Ql)r]- group is independently defined;
Rl, R2, R6, R7, R8, R9 independently represent a group selected from
15 hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl. aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7
20 and independently R8 together with R9 represent oxygen;
E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from hydroxy, mono- or polycarboxylate derivatives, aryl, heteroaryl, sulphonate, thiol (-RSH), thioethers (-R-S-R"), disulphides (-RSSR"),
25 dithiolenes, mono- or polyphosphonates, mono- or polyphosphates, electron donating groups andUlectron withdrawing groups, and groups of formulae (G"XG^N-, (G"XG2) (G3)N-, (GlXG2)N-C(O)- G3O- and G3C(O) wherein each of G1 G2 and G3 is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoing));
30 or one of R1-R9 is a bridging group bound to another moiety of the same general
formula;

WO 00/12667 PCT/GB99/02876

Tl and T2 independently represent groups R4 and R5, wherein R4 and R5 are as defined for R1-R9, and if g=0 and sX), Rl together with R4, and/or R2 together with RS, may optionally independently represent =CH-R10, wherein R10 is as defined for 5 Rl-R9,or
Tl and T2 may together (-T2-T1-) represent a covalent bond linkage when s>l andg>0;
if Zl and/or Z2 represent N and Tl and T2 together represent a single bond 10 linkage and Rl and/or R2 are absent, Q1 and/or Q2 may independently represent a group of the formula: =CH-[-Yl-]e-CH=,
optionally any two or more of Rl, R2, R6, R7, R8. R9 independently are linked together by a covalent bond; 15
if Zl and/or Z2 represents O, then Rl and/or R2 do not exist; If Zl and/or Z2 represents S, N, P, B or Si then Rl and/or R2 may be absent; if Zl and/or Z2 represents a heteroatom substituted by a functional group E then Rl and/or R2 and/or R4 and/or RS may be absent. 20
The groups Zl and 72 preferably independently represent an optionally substituted heteroatom selected from N, P, O, S, B and Si or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrimidines, pyrazine, pyramidine, pyrazole, pyrrole, imidazole, benzimidazole, 25 quinoleine, isoquinoline, carbazole, indole, isoindole, furane, thiophene, oxazole and thiazole. "
The groups R1-R9 are preferably independently selected from -H, hydroxy-C0-C20-alkyl, haIo-C0-C20-alkyl, nitroso, formyl-C0-C20-alkyl, carboxyl-C0-C20-alkyl and esters and 30 salts thereof, carbamoyl-C0-C20-alkyl, sulpho-C0-C20-alkyl and esters and salts thereof, sulphamoyl-C0-C20-alkyl, amino-C0-C20-alkyl, aryl-C0-C20-alkyl, heteroaryl-C0-C20-

WO 00/12667 PCT/GB99/02876
alkyl, C0-C20-alkyl, alkoxy-C0-C8-alkyl. carbonyl-C0-C6-alkoxy, and aryl-C0-C6-alkyl and C0-C20-alkylamide.
S One of R1-R9 may be a bridging group which links the ligand moiety to a second ligand moiety of preferably the same general structure. In this case the bridging group may have the formula -C-(R1l)(R12)-(D)p-Cm(R11(R12)- bound between the two moieties, wherein p is zero or one, D is selected from a heteroatom or a heteroatom-containing group, or is part of an aromatic or saturated homonuclear and heteronuclear
10 ring, n* is an integer from 1 to 4, m" is an integer from 1 to 4. with the proviso that
n"+m" 15 hetero atoms, in the same moiety, with the bridging group preferably being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge.
In a first variant according to formula (BI), the groups Tl and T2 together form a single bond linkage and s>l, according to general formula (BII):
20

wherein Z3 independently represents a group as defined for Zl or 22; R3 independently represents a group as defined for R1-R9; Q3 independently represents a group as 25 defined for Ql, Q2; h represents zero or an integer from 1 to 6; and s"=s-l.

WO 00/12667

PCT/GB99/02876

In a first embodiment of the first variant, in general formula (BIT), s"=l, 2 or 3; r=g=h=l; d=2 or 3; e=f=0; R6=R7=H, preferably such that the ligand has a general formula selected from:

10
15

20 and more preferably selected from:

25

30

In these preferred examples, Rl, R2, R3 and R4 are preferably independently selected from -H, alkyl, aryl, heteroaryl, and/or one of Rl -R4 represents a bridging group bound to another moiety of the same general formula and/or two or more of R1-R4 together represent a bridging group linking N atoms in the same moiety, with the bridging group

WO 00/12667 PCT/GB99/02876
being alkylene or hydroxy-alkylene or a heteroaiyl-containing bridge, preferably heteroarylene. More preferably, Rl, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with 5 the bridging group being alkylene or hydroxy-alkylene.
According to this first embodiment, in the complex preferably:

10 RCOO";
15
In a second embodiment of the first variant, in general formula (BIT), s"=2; r=g=h=l; d=f=0; e=l; and each Yl is independently alkylene or heteroarylene. The ligand preferably has the general formula: 20

wherein
A1,"A2, A3, A4 are independently selected from C1-9-alkylene or heteroarylene 25 groups; and
N1 and N2 independently represent a hetero atom or a heteroarylene group.

WO 00/12667 PCT/GB99/02876
In a preferred second embodiment, N1 represents an aliphatic nitrogen. N2 represents a
heteroarylene group, Rl, R2, R3, R4 each independently represent -H, alkyl, aryl or
heteroaryl, and A1, A2, A3, A4 each represent -CH2-.
5 One of R1-R4 may represent a bridging group bound to another moiety of the same general formula and/or two or more of R1-R4 may together represent a bridging group linking N atoms in the same moiety, with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge. Preferably, Rl, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyi, nitrogen-containing heteroaryl,
10 or a bridging group bound to another moiety of the same general formula or linking N atoms in the same moiety with the bridging group being alkylene or hydroxy-alkylene.
Particularly preferably, the ligand has the general formula:

15
20

wherein Rl, R2 each independently represent -H, alkyl, aryl or heteroaryl.
According to this second embodiment, in the complex [MaLkXn] Ym preferably:
25 M=Fe(II)-(III), Mn(IV), Cu(II), Co(II)-(III);
x= CH3CN, OH2, cr, Br", OCN, N3 SCN; OH-, O2, PO43-, C6H5BO22-,
RCOO-;
Y= €1O4, BPh4", Br C1 , [FeCl4,]", PF6 , NO3";
a=1,2,3,4;
30 n=0,1,2,3,4,5,6,7,8,9;
m=1,2,3,4; and k= 1,2,4.

WO 00/12667 PCT/GB99/02876

In a third embodiment of the first variant, in general formula (BII), s-=2 and r=g=h=l, according to the general formula:

10

In this third embodiment, preferably each Z1-Z4 represents a heteroaromatic ring; e=f=0; d=l; and R7 is absent, with preferably R1=R2=R3=R4= 2,4.6-trimethyl-3-SO3Na-phenyl, 2,6-diCl-3(or 4)-SO3Na-phenyl.
Alternatively, each Z1-Z4 represents N; R1-R4 are absent; both Q1 and Q3 represent =CH-[-Yl-]e-CH=; and both Q2 and Q4 represent-CH2-[-Yl-]n-CH2-

Thus, preferably the ligand has the general formula:

WO 00/12667 PCT/GB99/02876

wherein A represents optionally substituted alkylene optionally interrupted by a heteroatom; and n is zero or an integer from 1 to 5.
5 Preferably, R1-R6 represent hydrogen, n*l and A= -CH2, -CHOH-, -CH2N(R)CH2- or -CH2CH2N(R)CH2CH2- wherein R represents hydrogen or alkyl, more preferably A= -CH2-, -CHOH- or -CH2CH2NHCH2CH2-.
According to this third embodiment, in the complex [MaLkXn]Ym preferably:
10 M=Mn(II)r(IV),Co(II)-(III),Fe(II)-(III);
X= CH3CN, OH2, CI", Br", OCN, N3, SCN, OH", O2- PO43-, C6H5BO22; RCOO";
Y= C1O4, BPh4", Br", C1", [FeCl4]", PF6 *, NO3";
a=1,2,3,4;
15 n=0,1,2,3,4,5,6,7, 8,9;
m=1,2,3,4; and
k=1,2,4.
In a second variant according to formula (BI), Tl and T2 independently represent groups 20 R4, R5 as defined for Rl -R9, according to the general formula (BIII):

WO 00/12667 PCT/GB99/02876

Preferably, the ligand is selected from:
In a first embodiment of the second variant, in general formula (Bill), s=l; r=l; g=0; d=f=l; e=l-4; Yl= -CH2-; and Rl together with R4, and/or R2 together with R5, independently represent "CH-R10, wherein R10 is as defined for R1-R9, In one example, R2 together with R5 represents =CH-R10, with Rl and R4 being two separate groups. Alternatively, both Rl together with R4, and R2 together with RS may independently represent =CH-R10. Thus, preferred ligands may for example have a structure selected from:

WO 00/12667 PCT/GB99/02876
wherein Rl and R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, heteroaryl-C0-C20-alkyls, alkylaryl, aminoalkyl, alkoxy, more preferably Rl and R2 being selected from optionally substituted phenols, heteroaryl-C0-C2-alkyls, R3 and R4 5 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-Co-C2-alkyls.
According to this first embodiment, in the complex [MaLk„] Ym preferably:
M= Mn(II)-(IV), Co(II)-(III), Fe(III);
10 X= CH3CN, OH2, CI", Br, OCN, N3" SCN, OH-, O2", PO4,3- C6H5BO2.2"
RCOO-;
Y= C1O4, BPh4", Br C1," [FeCl4,]", PF6", NO3"; a= 1,2,3,4;
n= 0,1,2,3,4,5,6,7,8,9;
15 m= 1,2,3,4; and
k=l,2,4.
In a second embodiment of the second variant, in general formula (BIII), s=l; r=l; g=0; d=f=l; e=l-4; Yl= -C(R"XR"), wherein R" and R" are independently as defined for 20 R1-R9. Preferably, the ligand has the general formula:

The groups"Rl, R2, R3, R4, R5 in this formula are preferably -H or C0-C20-alkyl, n=0 or 1, R6 is -H, alkyl, -OH or -SH, and R7, R8, R9, R10 are preferably each independently selected from -H, C0-C20-alkyl, heteroaryl-C0-C20-alkyl, alkoxy-C0-C8-alkyl and amino-30 C0-C20-alkyl

WO 00/12667 PCT/GB99/02876
According to this second embodiment, in the complex [MaLkXn] Ym preferably: M= Mn(II)-(IV), Fe(II)-(III). Cu(II), Co(II)-(III)
X= CH3CN, OH2, CI, Br, OOP, N3 SCN OH", O2 PO43 C6H5BO22
RCOO";
5 Y- C1O4 BPh4 Br", CI", [FeCU]", PF6 NO;
-1,2.3,4; n=0,1,2,3,4; m= 0,1,2,3,4,5,6,7,8; and k=l,2,3,4.
10
More preferably, the ligand has the general formula: 20

In a third embodiment of the second variant, in general formula (BIII), s=0; g=l; d=e=0; f=l -4. Preferably, the ligand has the general formula:

wherein Rl, R2, R3 are as defined for R2, R4, R5.
25 According to this third embodiment, in the complex [MaLkXn] Ym preferably: M= Mna(II)-(IV), Fe(II)(III), Cu(II), Co(III); X= CH3CN, OH2, CI", Br, OCW, N3 SOT, OH",O2 PO43", C6H5BO22-,
RCOO";

WO 00/12667 PCT/GB99/02876

5
In a fourth embodiment of the second variant, the organic substance forms a complex of the general formula (A):
10
in which
M represents iron in the II, III,IV or V oxidation state, manganese in the II. III.
IV, VI or VII oxidation state, copper in the I, II or III oxidation state, cobalt in the II. Ill
15 or IV oxidation state, or chromium in the II-VI oxidation state;
X represents a coordinating species;
h represents zero or an integer in the range from 0 to 3;
z represents the charge of the complex and is an integer which can be positive,
zero or negative;
20 Y represents a counter ion, the type of which is dependent on the charge of the
complex;
q - z/[charge Y]; and
L represents a pentadentate ligand of the general formula (B):

25 R1 R2
wherein
each R1, R2 independently represents -R4-R5,

WO00/12«67 PCT/GB99/02876

R3 represents hydrogen, optionally substituted alkyl. aryl or arylalkyl. or -R4-R5,
each R4 independently represents a single bond or optionally substituted
alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or
carboxylic amide, and
5 each R5 independently represents an optionally N-substituted aminoalkyl group
or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.
The ligand L having the general formula (B), as defined above, is a pentadentate ligand. 10 By "pentadentate" herein is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex.
In formula (B), one coordinating hetero atom is provided by the nitrogen atom in the methylamine backbone, and preferably one coordinating hetero atom is contained in . 15 each of the four R1 and R2 side groups. Preferably, all the coordinating hetero atoms are nitrogen atoms.
The ligand L of formula (B) preferably comprises at least two substituted or unsubstituted heteroaryl groups in the four side groups. The heteroaryl group is
20 preferably a pyridin-2-yl group and, if substituted, preferably a methyl- or ethyl-substituted pyridin-2-yl group. More preferably, the heteroaryl group is an unsubstituted pyridin-2-yl group. Preferably, the heteroaryl group is linked to methylamine, and preferably to the N atom thereof, via a methylene group. Preferably, the ligand L of formula (B) contains at least one optionally substituted amino-alkyl side group, more
25 preferably two amino-ethyl side groups, in particular 2-(N-alkyl)amino-ethyl or 2-(N,N-dialkyl)amino-ethyl.

Thus, in formula (B) preferably R1 represents pyridin-2-yl or R2 represents pyridin-2-yl-methyl. Preferably R2 or R1 represents 2-amino-ethyl, 2-(N-(m)ethyl)amino-ethyl or 2-30 (N,N-di(m)ethyl)amino-ethyl. If substituted, Rs preferably represents 3-methyl pyridin-2-yl. R3 preferably represents hydrogen, benzyl or methyl.

WO 00/12667 PCT/GB99/02876

Examples of preferred ligands L of formula (B) in their simplest forms are:
(i) pyridin-2-yl containing ligands such as: 5 N.N-bis(pyridin-2-yl-methyl)bis(pyridin-2-yl)methylamine;
N,N-bis(pyrazol-l -yl-methyl)-bis(pyridin-2-yl)methylamine;
N,N-bis(imidazol-2-yl-methyl)-bis(pyridin-2-yl)methylamine;
N,N-bis(l,2,4-triazol-l-yl-methyl)-bis(pyridin-2-yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-bis(pyrazol-l-yl)methylamine; 10 N,N-bis(pyridin-2-yl-memyl)-bis(imidazol-2-yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-bis( 1,2,4-triazol-1 -yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-l.l-bis(pyridin-2-yl)-l-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-phenyl-1 -aminoethane;
N,N-bis(pyrazol-1 -yl-methyl)-1.1 -bis(pyridin-2-yI)-1 -aminoethane; 15 N,N-bis(pyrazol-1 -yl-methyl)-1.1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane;
N,N-bis(imidazol-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-l -aminoethane;
N,N-bis(imidazol-2-yl-methyl)l ,1 -bis(pyridin-2-yl)-2-phenyl-l -aminoethane;
N,N-bis(l,2,4-tria2ol-l-yl-methyl)-1,1-bis(pyridin-2-yl)-l-aminoethane;
N,N-bis(l ,2,4-triazol-1 -yl-methyl)-1,1 -bis(pyridin-2-yl)-2-phenyl-1 -aminoethane; 20 N,N-bis(pyridm-2-yl-methyl)-l,l-bis(pyrazol-l-yl)-l-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1.1 -bis(pyrazol-1 -yl)-2-phenyl-1 -aminoethane;
N,N-bis(pyridin-2-yl-methyl)-l ,1 -bis(imidazol-2-yl)-l -aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(imidazol-2-yl)-2-phenyl-1 -aminoethane;
N,N-bis(pyridin-2-yl-methyl)-l,l-bis(l,2,4-triazol-l-yl)-l-aminoethane; 25 N,N-bis(pyridin-2-yl-methyl)l,l-bis(l,2,4-triazol-l-yl)-l-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-1 -aminoethane;
N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-l-aminohexane;
N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-phenyl-l-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-(4-sulphonic acid-phenyl)-l-30 aminoethane;
N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-(pyridin-2-yl)-l-ammoethane;

WO 00/12667 PCT/GB99/02876

N,N-bis(pyridin-2-yI-methyl)-l,l-bis(pyridin-2-yl)-2-(pyridin-3-yl)-l-aminoe N,N-bis(pyridin-2-yl-methyl)-l-bis(pyridin-2yl)-2-(pyridin-4-yl)-1-aminoethane N,N-bis(pyridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-(1-alkyl-pyridinium-4-yl)-1-aminoethane; 5 N,N-bis(pyridin-2-yI-methyl)-1,1-bis(pyridin-2-yl)-2-(l-alkyl-pyridinium-3-yl)-1-aminoethane;
N,N-bis(pyridin-2-yl-methyl)-1,1 -bis(pyridin-2-yl)-2-( 1 -alkyl-pyridinium-2-yl)-1 -aminoethane;
10 (ii) 2-amino-ethyl containing ligands such as:
N,N-bis(2-(N-alkyl)amino-ethyl)-bis(pyridin-2-yl)methylamine;
N,N-bis(2-(N-alkl)amino-ethyl)-bis(pyrazol-l-yl)methylarnine;
N,N-bis(2-(N-alkyl)amino-ethyl)-bis(imidazol-2-yl)methylamine;
N,N-bis(2-(N-alkyl)amino-ethyl)-bis(l ,2,4-triazol-l -yl)methylamine; 15 N,N-bis(2-(N,N-alkyl)amino-ethyl)-bis(pyridin-2-yl)methylarnine;
N,N-bis(2-(N,N-dialkyl)amino-ethyl)-bis(pyrazol-1 -yl)methylamine;
N,N-bis(2-(N,N-alkyl)amino-ethyl)-bis(imidazol-2-yl)methylamine;
N,N-bis(2-(N,N-alkyl)amino-ethyl)-bis(l,2,4-triazol-l-yl)methylamine;
N,N-bis(pyridin-2-yl-methyl)-bis(2-amino-ethyl)methylamine; 20 N,N-bis(pyrazol-1 -yl-methyl)-bis(2-amino-ethyl)methylamine;
N,N-bis(imidazol-2-yl-methyl)-bis(2-amino-ethyl)methylamine;
N,N-bis(l,2,4-triazol-l-yl-methyl)-bis(2-amino-ethyl)methylamine.

More preferred ligands are: 25 N,N-bis(pyridin-2-yl-methyl)bis(pyridin-2-yl)methylamine, hereafter referred to as
N4Py.
N,N-bis(pyridin-2-yl-methyl)-l ,1 -bis(pyridin-2-yl)-l -aminoethane, hereafter referred to
as MeN4Py,
N,N-bis(pridin-2-yl-methyl)-l,l-bis(pyridin-2-yl)-2-phenyl-l-aminoethane, hereafter 30 referred to as BzN4Py.

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In an alternative fourth embodiment, the organic substance forms a complex of the
general formula (A) including a ligand (B) as defined above, but with the proviso that
R3 does not represent hydrogen.
5 In a fifth embodiment of the second variant, the organic substance forms a complex of the general formula (A) as defined above, but wherein L represents a pentadentate or hexadentate ligand of general formula (C):
R1R1N-W-NR1R2
10 wherein
each R1 independently represents -R3-V, in which R3 represents optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and IS thiazolyl;
W represents an optionally substituted alkylene bridging group selected from -CH2CH2",CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2-, and -CH2-C10H6-CH2-; and
R2 represents a group selected from R\ and alkyl, aryl and arylalkyl groups 20 optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy,
carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N*(R4)3, wherein R4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether and alkenyl ether.
25 The ligand L having the general formula (C), as defined above, is a pentadentate ligand or, if R1=R-, can be a hexadentate Iigand. As mentioned above, by "pentadentate" is meant that five hetero atoms can coordinate to the metal M ion in the metal-complex. Similarly, by "hexadentate1 is meant that six hetero atoms can in principle coordinate to the metal M ion. However, in this case it is believed that one of the arms will not be
30 bound in the complex, so that the hexadentate ligand will be penta coordinating.

WO 00/12667 PCT/GB99/02876
In the formula (C), two hetero atoms are linked by the bridging group W and one coordinating hetero atom is contained in each of the three R1 groups. Preferably, the coordinating hetero atoms are nitrogen atoms.
5 The ligand L of formula (C) comprises at least one optionally substituted heteroaiyl group in each of the three R1 groups. Preferably, the heteroaiyl group is a pyridin-2-yl group, in particular a methyl- or ethyl-substituted pyridin-2-yl group. The heteroaiyl group is linked to an N atom in formula (C), preferably via an alkylene group, more preferably a methylene group. Most preferably, the heteroaiyl group is a 3-methyl-10 pyridin-2-yl group linked to an N atom via methylene.
The group R2 in formula (C) is a substituted or unsubstituted alkyl, aryl or arylalkyl group, or a group R1. However, preferably R2 is different from each of the groups R1 in the formula above. Preferably, R2 is methyl, ethyl, benzyl. 2-hydroxyethyl or 2-15 methoxyethyl. More preferably, R2 is methyl or ethyl.
The bridging group W may be a substituted or unsubstituted alkylene group selected from -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2-, and -CH2-C10H6-CH2- (wherein -C6H4-, -C6H10-, -C10H6- can be ortho-,para-, or 20 meta-C6C4-, -C6H10-, -C10H6-). Preferably, the bridging group W is an ethylene or 1,4-butylene group, more preferably an ethylene group.
Preferably, V represents substituted pyridin-2-yl, especially methyl-substituted or ethyl-substituted pyridin-2-yI, and most preferably V represents 3-methyl pyridin-2-yl. 25
Examples of preferred ligands of formula (C) in their simplest forms are:
N-methyl-N,NNN"-tris(3-memyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-ethyl-N,N,NN"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine; 30 N-benzyl-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine; N-(2-hydroxyethyl)-N,N,,N,-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine

WO 00/12667 PCT/GB99/02876
N-(2-methoxyethyl)-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine;
N-methyl-N,NN"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l,2diamine; N-ethyl-N,N,N"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; 5 N-benzyl-N,N",N"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine;
N-(2-hydroxyethyl)-N,N"N"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-(2-methoxyethyl)-N,NN"-tris(5-methyl-pyridin-2-ylmethyl)ethylene-1.2diamine;
N-methyl-N,N,,N,-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine; 10 N-ethyl-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; N-benzyl-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l,2dimine; N-(2-hydroxyethyl)-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethy!ene-l,2-diamine; N-(2-methoxyethyl)-N,N,N"-tris(3-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine;
15 N-methy!-N,N"Nl"-tris(5-ethyl-pyridin-2-ylmethyl)ethyIene-l,2-diamine; N-ethyl-N,N",N"-tris(5-ethyl-pyridin-2-ylmethyl)ethyIene-l,2-diamine; N-benzy1-N,N,N"-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine; and N-(2-methoxyethyl)N,N,N"-tris(5-ethyl-pyridin-2-ylmethyl)ethylene-l,2-diamine.
20 More preferred ligands are:
N-methyl-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l,2-diamine;
N-ethyl-N,NN"-tris(3-methyl-pyridin-2-yImethyl)ethyIene-l,2-diamine;
N-benzyl-N,N"N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine;
N-(2-hydroxyethyl)-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-diamine; 25 and
N-(2-methoxyethyl)-N,N",N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-1,2-diamine
The most preferred ligands are:
N-methyl-N,N,N"-tris(3-methyl-pyridin-2-ylmethyl)ethylene-l ,2-diamine; and 30 N-ethyl-N,N,N"-tris(3-methyl-pyridin)-2-ylmethyl)ethylene-l,2diamine.

WO 00/12667 PCT/GB99/02876
Preferably, the metal M in formula (A) is Fe or Mn. more preferably Fe.
Preferred coordinating species X in formula (A) may be selected from R6OH. NR63, R6CN, R6OO", R6S", R60", R6COO", OCN", SCN", N3",CN", F, Cl", Br", T, O2", NO3", 5 NO2, SO42-, SO32, PO43- and aromatic N donors selected from pyridines, pyrazines, pyrazoles, pyrroles, imidazoles, benzimidazoles, pyrimidines, triazoles and thiazoles, with R6 being selected from hydrogen, optionally substituted alkyl and optionally substituted aryl. X may also be the species LMO or LMOO", wherein M is a transition metal and L is a ligand as defined above. The coordinating species X is preferably 10 selected from CH3CN, H2O, F, Cl, Br, OOH", R6COO", R6O", LMO", and LMOO" wherein R6 represents hydrogen or optionally substituted phenyl, naphthyl, or C1-C4 alkyl.
The counter ions Y in formula (A) balance the charge z on the complex formed by the 15 ligand L, metal M and coordinating species X. Thus, if the charge z is positive, Y may be an anion such as R7COO", BPh4", ClO4, BF4", PF6", R7SO3", R7SO4", SO42- NO3", F, C1", Br",or 1", with R7 being hydrogen, optionally substituted alkyl or optionally substituted aryl. If z is negative, Y may be a common cation such as an alkali metal, alkaline earth metal or (alkyl)ammonium cation. 20
Suitable counter ions Y include those which give rise to the formation of storage-stable solids. Preferred counter ions for the preferred metal complexes are selected from R7COO", CIO4", BET, PF6 R7SO3 (in particular CF3SO3"), R7SO4", SO42, NO3", F, CI", Br, and F, wherein R7 represents hydrogen or optionally substituted phenyl, 25 naphthyl or C1-C4 alkyl.
It will be appreciated that the complex (A) can be formed by any appropriate means, including in situ formation whereby precursors of the complex are transformed into the active complex of general formula (A) under conditions of storage or use. Preferably, 30 the complex is formed as a well-defined complex or in a solvent mixture comprising a salt of the metal M and the ligand L or ligand L-generating species. Alternatively, the

WO 00/12667 PCT/GB99/02876
catalyst may be formed in situ from suitable precursors for the complex, for example in a solution or dispersion containing the precursor materials. In one such example, the active catalyst may be formed in situ in a mixture comprising a salt of the metal M and the ligand L, or a ligand L-generating species, in a suitable solvent Thus, for example, 5 if M is iron, an iron salt such as FeSO4 can be mixed in solution with the ligand L, or a ligand L-generating species, to form the active complex. In another such example, the ligand L, or a ligand L-generating species, can be mixed with metal M ions present in the substrate or wash liquor to form the active catalyst in situ. Suitable ligand L-generating species include metal-free compounds or metal coordination complexes that 10 comprise the ligand L and can be substituted by metal M ions to form the active complex according the formula (A).
Therefore, in alternative fourth and fifth embodiments, the organic substance is a compound of the general formula (D):
15

in which
M" represents hydrogen or a metal selected from Ti, V, Co, Zn, Mg. Ca, Sr, Ba. 20 Na,K,and Li;
X represents a coordinating species;
a represents an integer in the range from 1 to 5;
b represents an integer in the range from 1 to 4;
c represents zero or an integer in the range from 0 to 5;
25 z represents the charge of the compound and is an integer which can be positive,
zero or negative;
Y represents a counter ion, the type of which is dependent on the charge of the compound;
q = z/[charge Y]; and
30 L represents a pentadentate ligand of general formula (B) or (C) as defined
above.

WO 00/12667 PCT/GB99/02876
In a fourth embodiment of the first variant, the organic substance comprises a macrocyclic iigand of formula (E):
5
wherein
Z1 and Z2 are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring 10 structure being substituted by one or more substituents;
Y1 and Y2 are independently selected from C, N, O, Si, P and S atoms;
A1 and A2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl) being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulphonate, phosphate, electron 15 donating groups and electron withdrawing groups, and groups of formulae (G1)G2)N-, G3OC(O) G3O- and G3C(O)-, wherein each of G1, G2 and G3 is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups (in addition to any amongst the foregoing);
i and j are selected from1 and 2 to complete the valency of the groups Y1 and 20 Y2;
each of Q1-Q4 is independently selected from groups of formula

25 wherein 10>a+b+O2 and d>=1;

WO 00/12667 PCT/GB99/02876
each Y3 is independently selected from -0-. -S-, -SO-, -S02-, -(G1)N- (wherein G1 is hereinbefore defined), -C(O)- arylene, heteroarylene, -P- and -P(O)-;
each of A3-A6 is independently selected from the groups hereinbefore defined for
A1 and A2; and
5 wherein any two or more of Al-A6 together form a bridging group, provided that
if A1 and A2 are linked without simultaneous linking also to any of A3-A6, then the bridging group linking A1 and A2 must contain at least one carbonyl group.
In the ligands of formula (E), unless specifically stated to the contrary, all alkyl, 10 hydroxyalkyl alkoxy, and alkenyl groups preferably have from 1 to 6, more preferably from 1 to 4 carbon atoms.
Moreover, preferred electron donating groups include alkyl (e.g. methyl), alkoxy (e.g. methoxy), phenoxy, and unsubstituted. monosubsthuted and disubstituted amine groups. 15 Preferred electron withdrawing groups include nitro. carboxy. sulphonyl and halo groups.
The ligands of formula (E) may be used in the form of complexes with an appropriate metal or, in some cases, in non-complexed form. In the non-complexed form, they rely
20 upon complexing with a metal supplied in the form of a separate ingredient in the
composition, specifically provided for supplying that metal, or upon complexing with a metal found as a trace element in tap water. However, where the ligand alone or in complex form carries a (positive) charge, a counter anion is necessary. The ligand or complex may be formed as a neutral species but it is often advantageous, for reasons of
25 stability or ease of synthesis, to have a charged species with appropriate anion.
Therefore, in an alternative fourth embodiment, the ligand of formula (E) is ion-paired with a counter ion, which ion-pairing is denoted by formula (F):

30

WO 00/12667 PCT/GB99/02876

wherein
H is an hydrogen atom;
Y is a counter anion, the type of which is dependent on the charge of the
complex;
5 x is an integer such that one or more nitrogen atoms in L is protonated;
z represents the charge of the complex and is an integer which can be positive or zero;
q=z/[charge of Y]; and
L is a ligand of formula (E) as defined above. 10
In a further alternative fourth embodiment, the organic substance forms a metal complex of formula (G) based on the ion pairing of formula (F) thus:
[Ms L]zYq
15
wherein L, Y, x, z and q are as defined for formula (F) above and M is a metal selected from manganese in oxidation states II-V, iron II-V, copper I-III, cobalt I-III, nickel I-III, chromium II-VI, tungsten IV-VI, palladium V, ruthenium II-IV, vanadium III-IV and molybdenum IV-VI.
20
Especially preferred are the complexes of formula (G) wherein M represents manganese, cobalt, iron or copper.
In a preferred fourth embodiment, the organic substance forms a complex of the formula 25 (H):

WO 00/12667

PCT/GB99/02S76

wherein M represents an Iron atom in oxidation state II or III. a manganese atom in oxidation state II, ID, IV or V, a copper atom in oxidation state I, II or III or a cobalt 5 atom in oxidation state n, III or IV, X is a group which is either a bridge or is not a bridge between iron atoms, Y is a counter ion, x and y being >=1,0= For the avoidance of doubt, ""==" means "greater than or equal to". 15
Preferably, in the complex of formula (H), M represents an iron atom in oxidation state II or III or aVanganese atom in oxidation state II, HI, IV, or V. Preferably the oxidation state of M is ,IIL
20 When M is iron, preferably the complex of formula (H) is in the form of a salt of iron (in oxidised state) dihalo-2,1 l-diazo[3.3](2,6)pyridinophane, dihalo-4-methoxy-2,l 1-diazo[3.3] (2,6) pyridinophane and mixtures thereof, especially in the form of the chloride salt

. WO 00/12667 PCT/GB99/02876
When M is manganese, preferably the complex of formula (H) is in the form of a salt of manganese (in oxidised state) N, N"-dimethyl-2,1 l-diazo[3.3](2,6)pyridinophane, especially in the form of the monohexafiuorophosphate salt. Preferably, X is selected from H2O, Off, O2", SH, S2 SO42-NR9R10, RCOO", 5 NR9R10R11, CI", Br", F", N3 and combinations thereof, wherein R9, R10 and R11 are independently selected from -H, C1-4 alkyl and aryl optionally substituted by one or more electron withdrawing and/or donating groups. More preferably, X is a halogen, especially a fluoride ion. In the formulae (F), (G) and (H), the anionic counter ion equivalent Y is preferably
10 selected from CI", Br, I", N03, C104 SCN", PF6-, RS03 RS04", CF3S03 BPh4", and OAc A cationic counter ion equivalent is preferably absent. In formula (H), R1 and R2 are preferably both hydrogen. R3 and R4 are preferably C1-4 alkyl, especially methyl. R5-R8 are each preferably hydrogen. According to the values of x and y, the aforementioned preferred iron or manganese
15 catalysts of formula (H) may be in the form of a monomer, dimer or oligomer. Without being bound by any theory, it has been conjectured that in the raw materia! or detergent composition state, the catalyst exists mainly or solely in monomer form but could be converted to dimer, or even oligomeric form, in the wash solution. The bleaching compositions according to the present invention may be used for laundry
20 cleaning, hard surfaces cleaning (including cleaning of lavatories, kitchen work surfaces, floors, mechanical ware washing etc.). As is generally known in the art, bleaching compositions are also employed waste-water treatment, pulp bleaching during the manufacture of paper, leather manufacture, dye transfer inhibition, food processing, starch bleaching, sterilisation, whitening in oral hygiene preparations and/or contact
25 lens disinfection. In the context of the present invention bleaching should be
understood as relating generally to the decolonisation of stains or of other materials

attached to or associated with a substrate. However, it is envisaged that the present invention can be applied where a requirement is the removal and/or neutralisation by an oxidative bleaching reaction of malodours or other undesirable components attached to 30 or otherwise associated with a substrate.

WO 00/12667 PCT/GB99/02876
In typical washing compositions the level of the organic substance is such that the in-use level is from l µM to 50mM, with preferred in-use levels for domestic laundry operations falling in the range 10 to 100 µM. Higher levels may be desired and applied in industrial bleaching processes, such as textile and paper pulp bleaching 5
Preferably, the aqueous medium has a pH in the range from pH 6 to 13, more preferably from pH 6 to 11, still more preferably from pH 8 to 11. and most preferably from pH 8 to 10, in particular from pH 9 to 10.
10 The bleaching composition of the present invention has particular application in detergent formulations, especially for laundry cleaning. Accordingly, in another preferred embodiment, the present invention provides a detergent bleach composition comprising a bleaching composition as defined above and additionally a surface-active material, optionally together with detergency builder.
15
The bleach composition according to the present invention may for example contain a surfacejactive material in an amount of from 10 to 50% by weight The surface-active material may be naturally derived, such as soap, or a synthetic material selected from anionic, nonionic, amphoteric, zwitterionic, cationic actives and mixtures thereof.
20 Many suitable actives are commercially available and are fully described in the
literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
Typical synthetic anionic surface-actives are usually water-soluble alkali metal salts of 25 organic sulphates and sulphonates having alkyl groups containing from about 8 to about 22 carbon atoms, the term "alkyl" being used to include the alkyl portion of higher aryl groups. Examples of suitable synthetic anionic detergent compounds are sodium and ammonium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced, for example, from tallow or coconut oil; sodium and ammonium 30 alkyl (C9-C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-C15) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil fatty acid monoglyceride

WO 00/12667 PCT/GB99/02876
sulphates and sulphonates; sodium and ammonium salts of sulphuric acid esters of higher (C9-C18) fatty alcohol alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and ammonium salts of 5 fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefins (C8-C10) with sodium bisulphite and those derived by reacting paraffins with SO2 and Cl2 and then hydrolysing with a base to produce a random sulphonate; sodium and ammonium (C7-C12) dialkyl sulphosuccinates; and olefin sulphonates, which term is used to describe material made by reacting olefins, 10 particularly (C10-C20) alpha-olefins, with SO3 and then neutralising and hydrolysing the reaction product The preferred anionic detergent compounds are sodium (C10-C15) alkylbenzene sulphonates, and sodium (C16-C18) alkyl ether sulphates.
Examples of suitable nonionic surface-active compounds which may be used, preferably 15 together with the anionic surface-active compounds, include, in particular, the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6-C22) phenols, generally"5-25 EO, ie. 5-25 units of ethylene oxides per molecule; and the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 2-30 EO. Other so-called nonionic surface-actives include 20 alkyl polyglycosides, sugar esters, long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
Amphoteric or zwitterionic surface-active compounds can also be used in the compositions of the invention but this is not normally desired owing to their relatively 25 high cost. If any amphoteric or zwitterionic detergent compounds are used, it is
generally in small amounts in compositions based on the much more commonly used synthetic anionic and nonionic actives.
The detergent bleach composition of the invention will preferably comprise from 1 to 15 30 % wt of anionic surfactant and from 10 to 40 % by weight of nonionic surfactant. In a

WO 00/12667 PCT/GB99/02876
further preferred embodiment, the detergent active system is free from C16-C12 fatty acid soaps.
The bleach composition of the present invention may also contains a detergency builder, 5 for example in an amount of from about 5 to 80 % by weight, preferably from about 10 to 60 % by weight
Builder materials may be selected from 1) calcium sequestrant materials, 2) precipitating materials, 3) calcium ion-exchange materials and 4) mixtures thereof.
10
Examples of calcium sequestrant builder materials include alkali metal polyphosphates, such as sodium tripolyphosphate; nitrilotriacetic acid and its water-soluble salts; the alkali metal salts of carboxymethyioxy succinic acid, ethylene diamine tetraacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, citric acid; and
15 polyacetal carboxylates as disclosed in US-A-4,144.226 and US-A-4,146,495.
Example"s of precipitating builder materials include sodium orthophosphate and sodium carbonate.
20 Examples of calcium ion-exchange builder materials include the various types of water-insoluble crystalline or amorphous aluminosilicates, of which zeolites are the best known representatives, e.g. zeolite A, zeolite B (also known as zeolite P), zeolite C, zeolite X, zeolite Y and also the zeolite P-type as described in EP-A-0,384,070.
25 In particular, the compositions of the invention may contain any one of the organic and inorganic builder materials, though, for environmental reasons, phosphate builders are preferably omitted or only used in very small amounts. Typical builders usable in the present invention are, for example, sodium carbonate, calcite/carbonate, the sodium salt of nitrilotriacetic acid, sodium citrate, carboxymethyioxy malonate, carboxymethyioxy
30 succinate and water-insoluble crystalline or amorphous aluminositicate builder

WO 00/12667 PCT/GB99/02876
materials, each of which can be used as the main builder, either alone or in admixture with minor amounts of other builders or polymers as co-builder.
It is preferred that the composition contains not more than 5% by weight of a carbonate 5 builder, expressed as sodium carbonate, more preferably not more than 2.5 % by weight to substantially nil, if the composition pH lies in the lower alkaline region of up to 10.
Apart from the components already mentioned, the bleach composition of the present invention can contain any of the conventional additives in amounts of which such
10 materials are normally employed in fabric washing detergent compositions. Examples of these additives include buffers such as carbonates, lather boosters, such as alkanolamides, particularly the monoethanol amides derived from palmkemel fatty acids and coconut fatty acids; lather depressants, such as alkyl phosphates and silicones; anti-redeposition agents, such as sodium carboxymethyl cellulose and alkyl or substituted
15 alkyl cellulose ethers; stabilisers, such as phosphonic acid derivatives (i.e. Dequest® types); fabric softening agents; inorganic salts and alkaline buffering agents, such as sodium sulphate and sodium silicate; and, usually in very small amounts, fluorescent agents; perfumes; enzymes, such as proteases, cellulases, lipases, amylases and oxidases; germicides and colourants.
20
Transition metal sequestrants such as EDTA, and phosphonic acid derivatives such as EDTMP (ethylene diamine tetra(methylene phosphonate)) may also be included, in addition to the organic substance specified, for example to improve the stability sensitive ingredients such as enzymes, fluorescent agents and perfumes, but provided
25 the composition remains bleaching effective. However, the composition according to the present invention containing the organic substance, is preferably substantially, and more preferably completely, devoid of transition metal sequestrants (other than the organic substance).
30 Whilst the present invention is based on the catalytic bleaching of a substrate by atmospheric oxygen or air, it will be appreciated that small amounts of hydrogen

WO 00/12667 PCT/GB99/02876

peroxide or peroxy-based or -generating systems may be included in the composition, if desired. Preferably, however, the composition will be devoid of peroxygen bleach or peroxy-based or -generating bleach systems.
5 The invention will now be further illustrated by way of the following non-limiting examples:

WO 00/12667 PCT/GB99/02876
EXAMPLES
Example 1
5 This example describes a synthesis of a catalyst according to formula (A): (i) Preparation of MeN4Py ligand:
The precursor N4Py.HClO4 was prepared as follows:
10 To pyridyl ketone oxim (3 g, 15.1 mmol) was added ethanol (15 ml), concentrated
ammonia solution (15 mL) and NH4OAC (1.21 g, 15.8 mmol). The solution was warmed until reflux. To this solution was added 4.64 g Zn in small portions. After the addition of all Zn, the mixture was refluxed for 1 hour and allowed to cool to ambient temperature. The solution was filtered and water (15 ml) was added. Solid NaOH was
15 added until pH» 10 and the solution was extracted with CH2Cl2 (3 x 20 ml). The organic layers were dried over Na2SO4 and evaporated until dryness. Bis(pyridin-2-yl)methylamme (2.39 g, 12.9 mmol) was obtained as a colourless oil in 86% yield, showing the following analytical characteristics: 1H NMR (360 MHz, CDCl3): δ 2.64 (s, 2H, NH2), 5.18 (s, 1H, CH), 6.93 (m, 2H,
20 pyridine), 7.22 (m, 2H, pyridine), 7.41 (m, 2H, pyridine), 8.32 (m, 2H, pyridine); ,3C NMR(CDC13): 5 62.19 (CH), 121.73 (CH), 122.01 (CH), 136.56 (CH), 149.03 (CH), 162.64 (Cq).
To picolylchloride hydrochloride (4.06 g, 24.8 mmol) was added, at 0°C, 4.9 ml of a 5N 25 NaOH solution. This emulsion was added by means of a syringe to bis(pyridin-2-yl)methylamine (2.3 g, 12.4 mmol) at 0°C. Another 5 ml of a 5N NaOH solution was added to this mixture. After warming to ambient temperature, the mixture was stirred vigorously for 40 hrs. The mixture was put in an ice bath and HClO4 was added until pH
WO 00/12667 PCT/GB99/02876
to ambient temperature, whereupon a light-brown solid precipitated which was collected by filtration and washed with cold water and air-dried (1.47 g).
From 0.5 g of the perchlorate salt of N4Py prepared as described above, the free amine 5 was obtained by precipitating the salt with 2N NaOH and subsequently by extraction with CH2Cl2. To the free amine was added under argon 20 ml of dry tetrahydrofuran freshly distilled from LLAlH4. The mixture was stirred and cooled to -70 °C by an alcohol / dry ice bath. Now 1 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mixture was allowed to warm to -20 °G and
10 now 0.1 ml of methyl iodide was added. The temperature was kept to -10 °C for 1 hour. Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue water was added and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried on sodium sulphate, filtered and evaporated giving 0,4 g residue. The residue was purified by crystallisation from ethyl
15 acetate and hexane giving 0.2 g of creamish powder (50% yield) showing the following analytical characteristics:
1H NMR(400 MHz, CDCl3): δ (ppm) 2.05 (s, 3H, CH3), 4.01 (s, 4H, CH2), 6.92 (m, 2H, pyridine), 7.08 (m, 2H, pyridine), 7.39 (m, 4H pyridine), 7.60 (m 2H, pyridine), 7.98 (d, 2H, pyridine), 8.41 (m, 2H pyridine), 8.57 (m, 2H, pyridine). I3C NMR (100.55
20 MHz, CDCl3): 6 (ppm) 21.7 (CH3), 58.2 (CH2), 73.2 (Cq), 121.4 (CH), 121.7 (CH), 123.4 (CH), 123.6 (CH), 136.0 (CH), 148.2 (Cq), 148.6 (Cq), 160.1 (Cq), 163.8 (Cq).
(ii) Synthesis of the complex l(MeN4Py)Fe(CH3CN)](C1O4)2, Fe(MeN4Py):
25 To a solution of 0.27 g of MeN4Py in 12 ml of a mixture of 6 ml acetonitrile and 6 ml methanol was added 350 mg Fe(C1O4)2.6H2O immediately a dark red colour formed. To the mix was added now 0.5 g of sodium perchlorate and a orange red precipitate formed immediately. After 5 minutes stirring and ultrasonic treatment the precipitate was isolated by filtration and dried in vacuo at 50°C. In this way 350 mg of an orange red
30 powder was obtained in 70% yield showing the following analytical characteristics:

WO 00/12667 PCT/GB99/02876
39
1H NMR (400 MHz, CD3CN): 8 (ppm) 2.15, (CH3CN), 2.28 (s, 3H, CH3), 4.2 (ab, 4H,
CH2), 7.05 (d, 2H, pyridine), 7.38 (m, 4H, pyridine), 7.71 (2t, 4H pyridine), 7.98 (t, 2H,
pyridine), 8.96 (d, 2H pyridine), 9.06 (in, 2H, pyridine).
UV/Vis (acetonitrile) [Xmax, nm (e, M"" cm-1)]: 381 (8400), 458 nm (6400).
5 Anal.Calcd for C25H26Cl2FeN6O8: C, 46.11; H, 3.87; N, 12.41; CI, 10.47; Fe, 8.25.
Found: C, 45.49; H, 3.95; N, 12.5; CI, 10.7; Fe, 8.12.
Mass-ESP (cone voltage 17V in CH3CN): m/z 218.6 [MeN4PyFe]2+; 239.1
[MeN4PyFeCH3CN2+.
10 Example 2
This example describes a synthesis of a catalyst according to formula (A):
(i) Synthesis of BzN4Py ligand: 15
To 1 g of the N4Py ligand prepared as described above, 20 ml of dry tetrahydrofuran freshly distilled from L1AIH4, was added under argon. The mixture was stirred and cooled to -70 °C by an alcohol / dry ice bath. Now 2 ml of 2.5 N butyllithium solution in hexane was added giving an immediate dark red colour. The mix was allowed to warm
20 to -20°C and now 0.4 ml of benzyl bromidide was added. The mixture was allowed to warm up to 25 °C and stirring was continued over night Subsequently 0.5 g of ammonium chloride was added and the mixture was evaporated in vacuo. To the residue water was added and the aqueous layer was extracted with dichloromethane. The dichloromethane layer was dried on sodium sulphate, filtered and evaporated giving 1 g
25 brown oily residue. According to NMR spectroscopy, the product was not pure but contained no starting material (N4Py). The residue was used without further purification.
(ii) Synthesis of the complex [(BzN4Py)Fe(CH3CN)l(C104)j, Fe(BzN4Py):
30
To a solution of 0.2 g of the residue obtained by the previous described procedure in 10
ml of a mixture of 5 ml acetonitrile and 5 ml methanol was added 100 mg

WO 00/12667 PCT/GB99;02876
40
Fe(ClO4)2.6H2O immediately a dark red colour formed. To the mix was added now 0.25 g of sodium perchlorate and ethylacetate was allowed to diffuse into the mixture overnight Some red crystals were formed which were isolated by filtration and washed with methanol. In this way 70 mg of a red powder was obtained showing the following
5 analytical characteristics:
1H NMR (400 MHz, CD3CN): 5 (ppm) 2.12, (s, 3H, CH3CN), 3.65 + 4.1 (ab, 4H, CH2), 4.42 (s, 2H, CH2-benzyl), 6.84 (d, 2H, pyridine), 7.35 (m, 4H, pyridine), 7.45 (m. 3 H, benzene) 7.65 (m, 4H benzene + pryidine), 8.08(m, 4H, pyridine), 8.95 (m, 4H pyridine).
10 UV/Vis (acetonitrile) [Xmax, nm (e, M"1 cm"1)]: 380 (7400), 458 nm (5500). Mass-ESP (cone voltage 17V in CH3CN): m/z 256.4 [BzN4Py]2+; 612 [BzN4PyFeC104]+
Example 3:
15
This example describes syntheses of catalysts according to formula (C):

AH reactions were performed under a nitrogen atmosphere, unless indicated otherwise.
All reagents and solvents were obtained from Aldrich or Across and used as received, 20 unless stated otherwise. Petroleum ether 40-60 was distilled using a rotavapor before
using it as eluent Flash column chromatography was performed using Merck silica gel
60 or aluminium oxide 90 (activity II-III according to Brockmann).1H NMR (300
MHz) and 13C NMR (75 MHz) were recorded in CDCl3, unless stated otherwise.
Multiplicities were addressed with the normal abbreviations using p for quintet. 25
Synthesis of.starting materials for ligand synthesis:
Synthesis of N-benzyl amino acetonitrile. N-benzyl amine (5.35 g, 50 mmol) was dissolved in a water: methanol mixture (50 mL, 1:4). Hydrochloric acid (aq., 30 %) 30 was added until the pH reached 7.0. Added was NaCN (2.45 g, 50 mmol). After cooling to 0 °C, formaline (aq. 35 %, 4.00 g, 50 mmol) was added. The reaction was followed by TLC (aluminium oxide; EtOAc: Et3N = 9:1) until benzylamine could be

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detected. Subsequently the methanol was evaporated in vacuo and the remaining oil "dissolved" in water. The aqueous phase was extracted with methylene chloride (3 x 50 mL). The organic layers were collected and the solvent removed in vacuo. The residue was purified by Kugelrohr distillation (p = 20 mm Hg, T = 120oG) giving N-benzyl 5 amino acetonitrile (4.39 g, 30 mmol, 60 %) as a colourless oil.
1H NMR: δ 7.37 - 7.30 (m, 5H), 3.94 (s, 2H), 3.57 (s, 2H), 1.67 (br s, 1H);
13C NMR: δ 137.74,128.58,128.46,128.37,127.98,127.62,117.60.52.24,36.19.
Synthesis of TV-ethyl amino acetonitrile. This synthesis was performed analogously to 10 the synthesis reported for N-benzyl amino acetonitrile. However, detection was done by
dipping the TLC plate in a solution of KMnO4 and heating the plate until bright spots
appeared. Starting from ethylamine (2.25 g, 50 mmol), pure TV-ethyl amino acetonitrile
(0.68 g, 8.1 mmol, 16 %) was obtained as a slightly yellow oil.
lH NMR: δ 3.60 (s, 2H), 2.78 (q, J= 7.1,2H). 1.22 (br s, 1H), 1.14 (t, J= 7.2,3H); 15 ,3CNMR: δ117.78,43.08,37.01,14.53.
Synthesis of TV-ethyl ethylene-l ,2-diamine. The synthesis was performed according to Hageman; J.Org.Chem.; 14; 1949; 616, 634, starting from N-ethyl amino acetonitrile.
20 Synthesis of TV-benzyl ethylene-l,2-diamine. Sodium hydroxide (890 mg; 22.4 mmol) was dissolved in ethanol (96 %, 20 mL), the process taking the better part of 2 hours. Added was N-benzyl amino acetonitrile (4,2.92 g, 20 mmol) and Raney Nickel (approx. 0.5 g). Hydrogen pressure was applied (p = 3.0 atm.) until hydrogen uptake ceased. The mixture was filtered over Cellite, washing the residue with ethanol. The filter
25 should not run dry since Raney Nickel is relatively pyrophoric. The Cellite containing the Raney Nickel was destroyed by putting the mixture in dilute acid, causing gas formation). The ethanol was evaporated in in vacuo and the residue dissolved in water. Upon addition of base (aq. NaOH, 5N) the product oiled out and was extracted with chloroform (3 x 20 mL). After evaporation of the solvent in vacuo the "H NMR showed
30 the presence of benzylamine. Separation was enforced by column chromatography (silica gel; MeOH: EtOAc: Et3N = 1:8:1) yielding the benzyl amine, followed by the

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solvent mixture MeOH : EtOAc: Et3N = 5:4:1. Detection was done by using aluminium oxide as a solid phase in TLC, yielding pure N-benzyl ethylene-l,2-diamine (2.04 g, 13.6 mmol, 69%).
1H NMR: δ 733 - 7.24 (m, 5H), 3.80 (s, 2H), 2.82 (t, J= 5.7,2H), 2.69 (t J-= 5.7. 5 2H),1.46(brs,3H);
13C NMR: 8 140.37,128.22,127.93,126.73,53.73,51.88,41.66.
Synthesis of 2-acetoxymethyl-5-methyl pyridine. 2,5-Lutidine (31.0 g, 290 mmol), acetic acid (180 mL) and hydrogen peroxide (30 mL, 30 %) were heated at 70-80 °C for
10 3hours. Hydrogen peroxide (24 mL, 30 %) was added and the subsequent mixture heated for 16 hours at 60-70 °C. Most of the mixture of (probably) hydrogen peroxide, water, acetic acid, and peracetic acid was removed in vacuo (rotavap, water bath 50 °C until p = 20 mbar). The resulting mixture containing the N-oxide was added dropwise to acetic anhydride heated under reflux. This reaction was highly exothermic, and was
15 controlled by the dropping speed. After heating under reflux for an hour, methanol was added dropwise. This reaction was highly exothermic. The resulting mixture was heated under reflux for another 30 minutes. After evaporation of the methanol (rotavap, 50 °C until p = 20 mbar), the resulting mixture was purified by Kugelrohr distillation (p = 20 mm Hg, T -150 °C). The clear oil that was obtained still contained acetic acid.
20 This was removed by extraction (CH2Cl2, NaHCO3 (sat)) yielding the pure acetate of 2-acetoxymethyl-5-methyI pyridine (34.35 g, 208 mmol, 72 %) as a slightly yellow oil. 1H NMR: δ 8.43 (s, 1H), 7.52 (dd, J = 7.8, J - 1.7,1H), 7.26 (d, J - 7.2,1H), 5.18 (s, 2H), 2.34 (s, 3H), 2.15 (s, 3H); 13CNMR: 8 170.09,152.32,149.39,136.74,131.98,121.14,66.31,20.39,17.66.
25
Synthesis of 2-acetoxymethyl-5-ethyl pyridine. This synthesis was performed
analogously to the synthesis reported for 2-acetoxymethyl-5-methyl pyridine. Starting
from 5-ethyl-2-methyl pyridine (35.10 g, 290 mmol), pure 2-acetoxymethyl-5-ethyl
pyridine (46.19 g, 258 mmol, 89%) was obtained as a slightly yellow oil.
30 1HNMR: δ 8.47 (s, 1H), 7.55 (d, J= 7.8,1H), 7.29 (d, J= 8.1,1H), 2.67 (q, J=
7.8,2H), 2.14 (s, 3H), 1.26 (t, J= 7.77,3H);

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13C NMR: 8 170.56,152.80,149.11,138.47,135.89,121.67,66.72.25.65,20.78, 15.13.
Synthesis of 2-acetoxymethyl-3-methyl pyridine. This synthesis was performed 5 analogously to the synthesis reported for 2-acetoxymethyl-5-methyl pyridine. The only difference was the reversal of the Kugelrohr distillation and the extraction. According to lH NMR a mixture of the acetate and the corresponding alcohol was obtained. Starting from 2,3-picoline (31.0 g, 290 mmol), pure 2-acetoxymethyl-3-methyl pyridine (46.19 g, 258 mmol, 89%. calculated for pure acetate) was obtained as a slightly yellow 10 oil.
1HNMR: δ 8.45 (d, J= 3.9,1H), 7.50 (d, J= 8.4,1H), 7.17 (dd, J= 7.8, J=4.8, 1H), 5.24 (s, 2H), 2.37 (s, 3H), 2.14 (s, 3H).
Synthesis of 2-hydroxymetbyl-5-methyl pyridine. 2-Acetoxymethyl-5-methyl 15 pyridine (30 g, 182 mmol) was dissolved in hydrochloric acid (100 mL. 4 N). The mixture was heated under reflux, until TLC (silica gel; triethylamine:ethyl acetate:petroleum ether 40-60 = 1:9:19) showed complete absence of the acetate (normally 1 hour). The mixture was cooled, brought to pH > 11, extracted with dichloromethane (3 x 50 mL) and the solvent removed in vacuo. Pure 2-20 hydroxymethyl-5-methyl pyridine (18.80 g, 152 mmol, 84 %) was obtained by Kugelrohr distillation (p = 20 mm Hg, T = 130 °C) as a slightly yellow oil. 1H NMR: δ 8.39 (s, 1H), 7.50 (dd, J= 7.8, J= 1.8,IH), 7.15 (d, J= 8.1,1H), 4.73 (s, 2H), 3.83 (br s, 1H), 2.34 (s, 3H);
13C NMR: 8 156.67,148.66,137.32,131.62,120.24,64.12,17.98. 25
Synthesis of 2-hydroxymethyl-5-ethyl pyridine. This synthesis was performed analogousr/to the synthesis reported for 2-hydroxymethyl-5-methyl pyridine. Starting from 2-acetoxymethyl-5-ethyl pyridine (40 g, 223 mmol), pure 2-hydroxymethyl-5-ethyl pyridine (26.02 g, 189 mmol, 85 %) was obtained as a slightly yellow oil. 30 1HNMR: δ 8.40(d, J=1.2, lH),7.52(dd, J=8.0, J=2.6, IH), 7.18 (d,J= 8.1, 1H), 4.74 (s, 2H), 3.93 (br s, 1H), 2.66 (q, J = 7.6,2H), 1.26 (t, J= 7.5,3H);

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l3C NMR: 5 156.67,148.00,137.87,136.13,120.27,64.07,25.67,15.28.
Synthesis of 2-hydroxymethyl-3-methyl pyridine. This synthesis was performed
analogously to the synthesis reported for 2-hydroxymethyl-5-methyl pyridine. Starting
from 2-acetoxymethyl-3-methyl pyridine (25g (recalculated for the mixture), 152
mmol), pure 2-hydroxymethyl-3-methyl pyridine (15.51 g, 126 mmol, 83 %) was
obtained as a slightly yellow oil.
1H NMR: δ 8.40 (d, J=4.5, 1H)), 7.47 (d, J= 12,1H), 7.15 (dd, J- 7.5, J= 5.1,
1H), 4.85 (br s, 1H), 4.69 (s, 1H), 222 (s, 3H);
13CNMR: 8 156.06,144.97,137.38,129.53,121.91,61.38,16.30.
(i) Synthesis of lieands:
Synthesis of N-methyl-N,N,N,-tris(pyridin-2-ylmethyI)ethylene-l,2-diamine (L1). The ligand L1 (comparative) was prepared according to Bernal, Ivan; Jensen, Inge Margrethe; Jensen, Kenneth B.; McKenzie, Christine J.; Toftlund, Hans; Tuchagues, Jean-Pierre; J.Chem.Soc.DaIton Trans.; 22; 1995; 3667-3676.
Synthesis of N-methyl-N,N,N,-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L2, MeTrilen). 2-Hydroxymethyl-3-methyI pyridine (5.00 g, 40.7 mmol) was dissolved in dichloromethane (30 mL). Thionyl chloride (30 mL) was added dropwise under cooling (ice bath). The resulting mixture was stirred for 1 hour and the solvents removed in vacuo (rotavap, until p= 20 mm Hg, T = 50 °C). To the resultant mixture was added dichloromethane (25 mL). Subsequently NaOH (5 N, aq.) was added dropwise until the pH (aqua) > 11. The reaction was quite vigorous in the beginning, since part of the thionyl chloride was still present N-methyl ethylene-1,2-diamine (502 mg, 6.8 mmol) and additional NaOH (5 N, 10 mL) were added. The reaction mixture was stirred at room temperature for 45 hours. The mixture was poured into water (200 mL), and the pH checked (> 14, otherwise addition of NaOH (aq. 5N)). The reaction mixture was extracted with dichloromethane (3 or 4 x 50 mL,-until no product could be detected by TLC). The combined organic phases were dried and the solvent

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removed in vacuo. Purification was enforced as described before, yielding N-methyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine as a slightly yellow oil. Purification was enforced by column chromatography (aluminium oxide 90 (activity II-III according to Brockmann); triethylamine: ethyl acetate: petroleum either 40-60 -5 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf ~ 0.9). The compound was eluted using ethylacetate : triethyl amine = 9:1. N-memyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L2,1.743 g, 4.30 mmol, 63 %) was obtained.
1H NMR: δ 8.36 (d, J = 3.0,3H), 7.40 - 7.37 (m, 3H), 7.11 -7.06 (m, 3H), 3.76 (s, 10 4H), 3.48 (s, 2H), 2.76 - 2.71 (m, 2H), 2.53 - 2.48 (m, 2H), 2.30 (s, 3H), 2.12 (s, 6H), 2.05 (s,3H);
13C NMR: 8 156.82,156.77,145.83,145.67,137.61,133.14,132.72,122.10, 121.88,62.32,59.73,55.19,51.87,42.37,18.22,17.80.
15 Synthesis of N-ethyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L3, EtTrilen). This synthesis is performed analogously to the synthesis for L2. Starting from 2-hydroxymethyl-3-methyl pyridine (25.00 g, 203 mmol) and N-ethyl ethylene-1,2-diamine (2.99 g, 34.0 mmol), N-ethyl-N,N,N",tris(methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L3,11.49 g, 28.5 mmol, 84 %) was obtained. Column
20 chromatography (aluminium oxide; Et3N : EtOAc: petroleum ether 40-60 = 1:9:30, followed by Et3N: EtOAc = 1:9).
1H NMR: δ 8.34 - 8.30 (m, 3H), 7.40 - 7.34 (m, 3H), 7.09 - 7.03 (m, 3H), 3.71 (s, 4H), 3.58 (s, 2H), 2.64 - 2.59 (m, 2H), 2.52 - 2.47 (m, 2H), 2.43 - 2.36 (m, 2H), 2.31 (s, 3H), 2.10 (s, 6H), 0.87 (t, J= 72,3H);
25 13C NMR: , δ 157.35,156.92,145.65,137.61,133.14,132.97,122.09,121.85,59.81, 59.28,51.98; 50.75,48.02,18.27,17.80,11.36.
Synthesis of N-benzyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L4, BzTrilen). This synthesis is performed analogously to the synthesis for 30 L2. Starting from 2-hydroxymethyI-3-methyIpyridine (3.00 g 24.4 mmol), and N-benzyl ethylene-1,2-diamine (610 mg, 4.07 mmol), N-benzyl-N,N,N"-tris(3-methylpyridin-2-

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ylmethyl)ethylene-l,2-diamine (L4,1.363 g, 2.93 mmol, 72 %) was obtained. Column chromatography (aluminium oxide; Et3N: EtOAc: petroleum ether 40-60 = 1:9:10). 1H NMR: δ 8.33 - 8.29 (m, 3H), 7.37 - 7.33 (m, 3H), 7.21 - 7.03 (m, 8H), 3.66 (s, 4H), 3.60 (s, 2H), 3.42 (s, 2H), 2.72 - 2.67 (m, 2H), 2.50 - 2.45 (m, 2H),2 23 (s, 3H), 5 2.03 (s, 6H);
13C NMR: 8 157.17,156.96,145.83,145.78,139.29,137.91,137.80,133.45, 133.30,128.98,127.85,126.62,122/28,122.22,59.99,58.83,51.92,51.54.18.40, 17.95.
10 Synthesis of N-hydroxyethyl-N,NN"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L5). This synthesis is performed analogously to the synthesis for L6. Starting from 2-hydroxymethyl-3-methyl pyridine (3.49 g, 28.4 mmol), and N-hydroxyethyl ethylene-1,2-diamine (656 mg 6.30 mmol), after 7 days N"-hydroxyethyl-N,N,N"tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L5,379 mg, 0.97 mmol. 14 %) was
15 obtained.
1H NMR: δ 8.31 - 8.28 (m, 3H), 7.35 - 7.33 (m, 3H), 7.06 - 7.00 (m, 3H), 4.71 (br s, 1H), 3.73 (s, 4H), 3.61 (s, 2H), 3.44 (t, J= 5.1,2H), 2.68 (s, 4H), 2.57 (t, J= 5.0,2H), 2.19 (s,3H), 2.10 (s,6H); 13C NMR: 8 157.01,156.88,145.91,145.80,137.90,137.83,133.30,131.89,
20 122.30,121.97,59.60,59.39,57.95,56.67,51.95,51.22,18.14,17.95.
Synthesis of iV-methyl-N,N,N"-tris(5-methylpyridin-2-yimethyl)ethylene-l^-diamine (L6). 2-hydroxymethyI-5-methyl pyridine (2.70 g, 21.9 mmol) was dissolved in dichloromethane (25 mL). Thionyl chloride (25 mL) was added dropwise under
25 cooling (ice bath). The resulting mixture was stirred for 1 hour and the solvents
removed in vacuo (rotavap, until p = 20 mm Hg, T + 35°C). The remaining oil was used directly in the synthesis of the ligands, since it was known from the literature that the free picolyl chlorides are somewhat unstable and are highly lachrymatory. To the resultant mixture was added dichloromethane (25 mL) and N-methyl ethylene-1,2-
30 diamine (360 mg, 4.86 mmol). Subsequently NaOH (5 N, aq.) was added dropwise. The reaction was quite vigorous in the beginning, since part of the thionyl chloride was

. WO 00/12667 PCT/GB99/02876
still present. The aqueous layer was brought to pH = 10, and additional NaOH (5 N. 4.38 mL) was added. The reaction mixture was stirred until a sample indicated complete conversion (7 days). The reaction mixture was extracted with dichloromethane (3 x 25 mL). The combined organic phases were dried and the solvent 5 removed in vacuo. Purification was enforced by column chromatography (aluminium oxide 90 (activity 11-111 according to Brockmann); triethylamine: ethyl acetate: petroleum ether 40-60 = 1:9:10) until the impurities were removed according to TLC (aluminium oxide, same eluent, Rf= 0.9). The compound was eluted using ethyl acetate : triethyl amine = 9:1, yielding N-methyl-N,N,N"-tris(5-methyIpyridin-2-
10 ylmethyl)ethylene-1,2-diamine (L6,685 mg, 1.76 mmol, 36 %) as a slightly yellow oil. 1HNMR: δ 8.31 (s, 3H) 7.43- 7.35 (m,5H), 7.21 (d,j= 7.8,1H), 3.76 (s, 4H), 3.56 (s, 2H), 2.74 - 2.69 (m, 2H), 2.63 - 2.58 (m, 2H), 2.27 (s, 6H), 2.16 (s, 3H); 13CNMR: 5 156.83,156.43,149.23,149.18,136.85,136.81,131.02,122.41, 122.30,63.83,60.38,55.53,52.00,42.76,18.03.
15
Synthesis of N-methyI-N,N,N"-tris(5-ethylpyridin-2-ylmethyl)ethyiene-l,2-diamine (L7). This synthesis is performed analogously to the synthesis for L6. Starting from 2-hydroxymethyl-5-ethyl pyridine (3.00 g, 21.9 mmol), and N-methyl ethylene-1,2-diamine (360 mg, 4.86 mmol), after 7 days N-methyl-N,N,N"-tris(5-ethyIpyridin-2-
20 ylmethyl)ethylene-l ,2-diamine (L7,545 mg, 1.26 mmol, 26 %) was obtained.
1H NMR: δ 8.34 (s, 3H), 7.44 - 7.39 (m, 5H), 7.26 (d, J = 6.6,1H), 3.80 (s, 4H), 3.59 (s, 2H), 2.77 - 2.72 (m, 2H), 2.66 - 2.57 (m, 8H), 2.18 (s, 3H), 123 (t, J= 7.5,9H); 13C NMR: 8 157.14,156.70,148.60,148.53,137.25,135.70,122.59,122.43,63.91, 60.48,55.65,52.11,42.82,25.73,15.36.
25
(jj) Synthesis of metal-ligand complexes:
Synthesis of N-methyl-N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-30 diamine iron(II)chloride.PF6([L2 Fe(II)CIIPF6). FeCl24H2O(51.2mg,257 umol) was dissolved in MeOH: H2O = 1:1 (2.5 mL). The solution was heated to 50 °C.

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Added was N-methyl-N,N,N;-tris(3-methylpyridin-2-ylmethyl)ethylene-1,2-diamine (L2,100 mg, 257 umol) in MeOH : H20 = 1:1 (2.0 mL). Subsequently NaPF6 (86.4 mg, 514 umol) in H2O (2.5 mL) was added dropwise. Cooling to room temperature, filtration and drying in vacuo (p = 0.05 mm Hg, T = room temperature)yielded "the 5 complex [L2 Fe(H)CI]PF6 (149 mg, 239 µmol, 93 %) as a yellow solid.
1H NMR (CD3CN, paramagnetic): δ 167.17,142.18,117.01,113.34,104.79,98.62, 70.77,67.04,66.63,58.86,57.56,54.49,51.68,48.56,45.90,27.99,27.36,22.89, 20.57,14.79,12.14,8.41,8.16,7.18,6.32,5.78,5.07,4.29,3.82,3.43.2.91,2.05,1.75, 1.58,0.94,0.53, -0.28, -1.25, -4.82, -18.97, -23.46.
10
Synthesis of N-ethyl-N,N,N"-tris(3-raethylpyridin-2-yImethyl)ethylene-l,2-diamine iron(II)chloride.PF6 ([L3 Fe(II)CI]PF6). This synthesis was performed analogously to the synthesis for [L2 Fe(II)Cl]PF6. Starting from N-ethyl N,N,N"-tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L3,104 mg, 257 umol) gave the complex [L3
15 Fe(II)Cl]PF6 (146 mg, 229 umol, 89%) as a yellow solid.
1H NMR (CD3CN, paramagnetic): δ 165.61,147.20,119.23,112.67,92.92,63.14, 57.44,53.20,50.43,47.80,28.59,27.09,22.48,8.55,7.40,3.63,2.95,2.75,2.56,2.26, 1.75,1.58,0.92,0.74,-0.28, -1.68, -2.68, -12.36, -28.75.
20 Synthesis of iV-benzyl-N,N,N",-tris(3-methylpyridin-2-ylniethyl)ethylene-l,2-diamine iron(II)chloride.PF6( ([L4 Fe(II)Cl]PF6). This synthesis was performed analogously to the synthesis for [L2 Fe(II)Cl]PF6. Starting from N-benzyl-N,N,N" tris(3-methylpyridin-2-ylmethyl)ethylene-l,2-diamine (L4,119.5 mg, 257 umol) gave the complex (172 mg, 229 umol, 95 %) as a yellow solid.
25 1H NMR (CD3CN, paramagnetic): 8 166.33,145.09,119.80,109.45,92.94,57.59, 52.83,47.31,28.40,27.89,16.28,11.05,8.70,8.45,7.69,6.99,6.01,4.12,2.89,2.71, 1.93,1.56, -0.28, -1.68, -2.58, -11.40, -25.32.
Example 4
30
This example describes a synmesis of a catalyst of formula (H) wherein:-

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(i) Synthesis of the ligand 2,ll-diaza[3,3]-(4-methoxv)(2,6)vvridinoyhane ((4OMe)LNIH2):
10 4-chloro-2.6-pvridvl dimethyl ester (2). A mixture of 4-hvdroxv-2.6-pyridine
dicarboxylic acid (12.2 g, 60 mmoles) and PC15 (41.8g, 200 mmoles) in 100 ml of CC14 was refluxed until the evolution of HC1 ceased. Absolute methanol (50ml) was slowly added. After cooling, all the volatile material was removed. The mixture was then poured into 200 ml of water and ice. The diester crystallised immediately and was
15 collected by filtration (70%). 1H NMR (200MHZ, H2O) δ 7.60 (2H,s), 4.05 (6H, s).
4-methoxy-2.6-pyridine dimethanol (4). Metallic sodium (lg, 44 mmoles) was dissolved into 200 ml of dry methanol. 4-chloro-2,6-pyridyl dimethyl ester (9.2 g, 40 mmoles) was then added and the mixture was refluxed for 3 hours to obtain pure 4-methoxy-2,6-

20 pyridyl dimethyl ester. To this solution, at RT, NaBH4 (9.1 g, 240 mmoles) was added in small portions and the mixture was refluxed for 16 hours. Acetone (30 ml) was then added and the solution refluxed for an additional 1 hour. After ail the volatile material was removed, the residue was heated with 60 ml of a saturated NaHCO3/Na2CO3 solution. After dilution with 80 ml of water, the product was continuously extracted

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with CHCl3 for 2-3 days. Evaporation of the CHC13 yielded 83 % of 4-methoxy-2,6-
pyridine dimethanol. 1HNMR (200MHZ, H20) δ 6.83 (2H,s), 5.30 (2H,s), 4.43 (4Hs),
3.82 (3H, s).
5 4-methoxy-2.6-dichloromethylpridine (5). This synthesis is carried out according literature.
N.N"-ditosyl-2.11-diaza[3.3[(4-methoxy)(2,Siuvridinophane. the procedure is similar to that described in the literature. The crude product obtained is practically pure 10 (yield=95%.)
1H-NMR (CDCl3,250 MHz): 7.72 (4H, d, J= 7Hz), 7.4 (1H, t, J= 6Hz), 7,35 (4H, d, J= 7Hz), 7.1 (1H, d, J= 6Hz), 6.57 (2H, s), 4.45 (4H, s), 4.35 (4H, s), 3.65 (3H, s), 2.4 (6H, s).
15 2,1 }-diazaf3.3 ](4-methoxy)(2,6)pyridinophane. The procedure is similar to the one
described previously. The crude product obtained is purified by chromatography
(alumina, CH2Cl2/MeOH 95:5), yield = 65%.
1H-NMR (CDCl3,250 MHz): 7.15 (1H, t, J= 6Hz), 6.55 (1H, d, J= 6Hz), 6.05 (2H, s),
3.95 (4H, s), 3.87 (4H, s), 3.65 (3H, s). 20 Mass spectrum (EI): M+ = 270 (100%)
(ii) Synthesis of the complex rFef4QMeLN,iHV>CMCl:
270 mg of 2,1 l-diaza[3.3]-(4-methoxyX2,6)pyridmophane (1 mmole) were dissolved in 25 15 ml of dry THF. To this solution was added a solution of 270 mg of FeCl3-6H2O (1 mmoles) in 5 ml of MeOH. The resulting mixture is evaporated to dryness and the solid product is dissolved in 10 ml of AcN with a minimum of MeOH. Slow diffusion of THF give 300 mg of brown crystals, yield = 70%. Elemental analysis for
C15H18N4Cl3OFe-0,5MeOH (found/theoretical): C=41.5/41.61 H=4.46/4.52 30 N=12.5/12.08

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IR (KBr pellets, cm"1): 3545,3414,3235,3075,2883,1615,1477,1437,1340,1157, 1049,883,628,338.
Example 5:
This example describes a synthesis of a catalyst of formula (H) wherein:-

10 R1-R8=H; x-1; y=l; z=l; X=C1, n=2; Y=C1", p=l
Synthesis of the complex [Fe(LN4H2)Cl2]CI:

15

240 mg of LN4H2 (1 mmoles) were dissolved in 15 ml of dry THF. To this solution was added a solution of 270 mg of FeCl3-6H2O (1 mmole) in 5 ml of MeOH. The resulting mixture is stirred and gives spontaneously 340 mg of yellow powder, yield = 85%IR (KBr pellets, cm"1): 3445,3031,2851,1629,1062,1473,1427,1335, 1157,1118,1045,936,796,340,318

20

Example 6:
This Example describes a synthesis of a catalyst of formula (H) wherein:-

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R1=R2=R5-8=H; R3=R4=Me; x=l; y=l; n=2; 2=1; X=F; m=2; Y=PF6; p=l
diflouro[N,N"dimethyl-2,11]-diazar3](2.6)DvridinophaneImamanese(IJJ) hexafluorophosphate.
10 (i) Synthesis of the ligand N.N"dimethyl-2.11-diaza[3.31(2.6)pyridinophane:
2.6-dichloromethylpyridine. A mixture of 2,6-dimethanolpyridine (5g, 36 ramoles) and
75 ml of SOl2 was refluxed for 4 hours. The mixture was concentrated (half volume).
Toluene was added (50 ml). The solid formed after cooling was then filtered and
15 dissolved in water and the solution neutralised with NaHCO3. The solid obtained is
filtered and dried (65%). 1H NMR (200MHZ, CDCl3) δ 7.8 (lH,t, J=7Hz), 7.45 (2H,d, J=7Hz),4.7(4H,s).
Sodium v-toluenesulphonamidure. To a mixture of Na° in dry EtOH (0.7 g, 29 mmolcs) 20 was added/7-toluenesulphonamide (5 g, 29 mmoles) and the solution was refluxed for 2 hours. After cooling, the solid obtained was filtered, washed with EtOH and dried (quantitative yield).
N.N"-ditosyl-2, J 1-diaza[3.3](2.6)pyidinophane. To a solution of sodium p-
25 toluenesulphonamidure (1.93 g, 10 mmoles) in 200 ml of dry DMF at 80°C was slowly
added 2,6-dichloromethylpyridine (1.76 g, 10 mmoles). After 1 hour a new portion of
sodium p-toluenesulphonamidure was added (1.93 g) and the final mixture stirred at

WO 00/12667 PCT/GB99/02876
80°C for an addition 4 hours. The solution was then evaporated to dryness. The solid obtained was washed with water and then with EtOH and finally crystallised in an CHCl3/MeOH mixture. The solid obtained is filtered and dried. The yield of (15) was 55 %. 1H NMR (200MHz, CDC13) δ 7.78 (4H,d, J=6Hz), 7,45 (6H,m), 7,15 ( 4Hd, 5 J=6Hz), 4.4 (8H, s), 2.4 (6H,s)
2.11-diaza[33](2.6)pvridinonhane. A mixture of N,N"-ditosyl-2.11-diaza[3.3] (2,6)pyridinophane (1.53 g, 2.8 mmoles) and 14 ml of H2SO4 90 % was heated at 110°C for 2 hours. The solution, cooled and diluted with 14 ml of water, was then carefully 10 poured into a saturated NaOH solution. The solid formed is extracted with chloroform. The organic layer is evaporated to dryness to yield 85 % of 2,ll-diaza[3.3](2,6)pyridinophane. 1H NMR (200MHz, CDCl3) δ 7.1 (2H,t, J=7Hz), 6.5 (4H,d, J=7 Hz), 3.9 (8H, s).
15 N,N"-dimethyl-2,11-diaza[3.3](2.6)pyidinophane. A mixture of 2,ll-diaza[3.3] (2,6)pyridinophane (0.57 g, 2.4 mmoles), 120 ml of formic acid and 32 ml of formaldehyde (32% in water) was refluxed for 24 hours. Concentrated HC1 (10 ml) were added and the solution evaporated to dryness. The solid was dissolved in water and basified with NaOH 5M, and the resulting solution was extracted with CHC13. The solid
20 obtained was purified by chromatography on alox (CH2Cl2+ t% MeOH) to yield 51 % of N,N-dimethyl-2,11-diaza[3.3](2,6)pyridinophane. 1H NMR (200MHz, CDCl3) 8 7.15 (2H,t, J=7Hz), 6.8 (4H,d, J=7 Hz), 3.9 (8H, s), 2.73 (6H,s).
(ii) Synthesis of the complex;
MnF3 (41.8 mg, 373 mmoles) was dissolved in 5 ml of MeOH, and N,N"-dimethyl-2,11-

diaza[3.3](2,6)pyridinophane (0.1 g, 373 mmoles) was added with 5 ml of THF. After 30 minutes of stirring at RT, 4 ml of THF saturated in NBu4PF6 were added, and the solution left without stirring until the crystallisation was finished. The product was 30 collected by filtration to yield 80% of complex. Elemental analysis (found, theoretical): %C (38.35, 37.94), %N (11.32, 11.1), %H (3.75, 3.95). IR (KBr pellet, cm-1): 3086,

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2965,2930,2821,1607, 1478,1444,1425,1174,1034. 1019, 844, 796, 603r 574. 555. UV-Vis (CH3CN, X in nm, E): 500, 110; 850, 30; (CH3CN/H20:1/1, X in nm, e): 465, 168; 850,30.
5 Example 7:
Bleaching of tomato-oil stained cloths without and with addition of [Fe(MeN4Py)(CH3CN)](ClO4)2, immediately after the wash (t=0) and after 24 h storage (t=l day).
10 In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/1 LAS (linear alkylbenzene sulphonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/1 LAS, tomato-soya oil stained cloths (6x6 cm) were added and stirred for 30 minutes at 30 °C. In a second series of experiments, the same tests were done in the presence of 10 µM [Fe(MeN4Py)CH3CN)](C1O4)2. referred to in the table below as
15 Fe(MeN4Py).
After the wash, the cloths were dried in a tumble drier and the reflectance was measured with a Minolta 3700d spectrophotometer at 460 nm. The difference in reflectance before and after the wash is defined as AR460 value. 20
The cloths were measured immediately after the wash (t=0), and after 24 h storage in a dark room under ambient conditions (t=ld). The results obtained are listed in the table below:

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Example 8:
Bleaching of tomato-oil stained cloths without and with addition of various metal catalysts measured immediately after drying.
5 In an aqueous solution containing 10 mM carbonate buffer (pH 10) without and with 0.6 g/l LAS (linear alkylbenzene sulphonate) or containing 10 mM borate buffer (pH 8) without and with 0.6 g/l LAS, tomato-soya oil stained cloths were added and kept in contact with the solution under agitation for 30 minutes at 30 °C. In comparative experiments, the same experiments were done by addition of 5 µM of dinuclear or 10 10 uM mononuclear complex, referred to in the table below.
After the wash, the cloths were rinsed with water and subsequently dried at 30 °C and the change in colour was measured immediately after drying with a Linotype-Hell scanner (ex Linotype). The change in colour (including bleaching) is expressed as the 15 AE value. The measured colour difTerence (AE) between the washed cloth and the unwashed cloth is defined as follows:
ΔE = [ΔL)2 +(Δa)2 +(Δb)2 ]1/2
20 wherein AL is a measure for the difference in darkness between the washed and unwashed test cloth; Aa and Ab are measures for the difference in redness and yellowness respectively between both cloths. With regard to this colour measurement technique, reference is made to Commission International de rEclairage (CIE); Recommendation on Uniform Colour Spaces, colour difference equations, psychometric
25 colour termsL supplement no 2 to CIE Publication, no 15, Colormetry, Bureau Central de la CIE, Paris 1978.
The following complexes were used:
30 i) [Mn2(l,4,7-trimethyl-l,4,7-triazacyclononane)2(µ0)3](PF6)2(l) Synthesized according to EP-B-458397;

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ii) [Mn(LN4Me2)] (=difluoro[N,N,dimethyl-2,ll-diaza[3.3](2,6)pyridinophane] manganese(III)hexafluorophosphate) (2)
Synthesized as described previously; 5
iii) [Fe(OMe)LN4H2)Cl2] (=Fe(2,l l-diaza[3.3]-(4-methoxy(2,6)pyridinophane)Cl2
(3)
Synthesised as described previously;
10 iv) C12-CoCo(4)
Synthesised according to EP-A-408131;
v) Me2CoCo(5)
Synthesised according to EP-A-408131; 15
vi) [Fe(tpen)](C104)2(6)
Syfithesised according to WO-A-9748787;
vii) [Fe(N,N,N,-tris(pyridin-2ylmethyl)-N-methyl-l ,2-€thylenediamine)Cl](PF6)2 (7)
20 Synthesised according to I. Bernal, el al, J. Chem. Soc, Dalton Trans. 22, 3667
(1995);
viii) [Fe2(N,N,N"-tetrakis(benzimidazol-2-ylmethyl)-propan-2-ol-l 3-diamine)(µ-
OH)NO3)2](NO3)2(8)
25 Synthesised according to Brennan, et al, Inorg. Chem., 30,1937 (1991);
ix) [Mn2(tpen)µ-O)2(µ-OAc)](ClO4)2(9)
Synthesised according to Toftlund, R; Markiewicz, A.; Murray, K.S.; Acta Chem. Scamd, 44, 443 (1990);

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x) [Mn(N.NN"-tris(pyridin-2-ylmethy)N"-methyl-l,2-ethylenediamine)Cl](PF6)
(10)
Synthesised as follows:
To a solution of manganese chloride tetrahydrate m tetrahydrofuran xi) [Mn2(N,N"-bis(pyridin-2-ylmethy)-l,2-ethylenediamine)2(µ-O)2](ClO4)3(11) Synthesised according to Glerup, J.; Goodson, P. A.: Hazett, A.; Hazell, R.: 15 Hodgson, D. J.; McKenzie, C. J.; Michelsen, K.; Rychlewska, U.; Toftlund, H. Inorg. Chem. (1994), 33(18), 4105-11;
xii) [Mn(N,N"-bis(pyridin-2-ylmethyl)N,N,-dimethyl-1,2-ethyIenediamine)2Cl2] (12)
Synthesised as follows:
20 Triethylamine (0.405g, 4 mmol) was a solution of salt of the ligand
bispicen(NMe) (0.416g, 1 mmol) in tetrahydrofuran anhydrous (10 mL) (ref ligand: C.
Li, et al, J. Chem. Soc, Dalton Trans. (1991), 1909-14). The mixture was stirred at
room temperature for 30 minutes. A few drops of methanol were added. The mixture
was filtered. Manganese chloride (0.198g, 1 mmol) dissolved in THF (1 mL) was added 25 to the mixture to give, after a stirring of 30 minutes, a white precipitate. The solution
was filtered, the filtrate was washed twice with dry ether and dried under vacuum. This
gave 0.093g of complex (23% yield).
xiii) [Mn2(N,N,N"N"-tetrakis(pyridin-2-ylmethyl)-propan-1,3-diamine)(µ,-O)(µ-30 OAc)2](C1O4)2(13)
Synthesised as follows:

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58 To a stirred solution of 6.56 g 2-chloro-methylpyridine (40 mmol) and 0.75 ml 1,3-propanediamine (9 mmol) in 40 ml water, is added slowly at 70°C over a period of 10 minutes, 8 ml 10M NaOH-solution, The colour of the reaction turned from yellow to deep red. The reaction was stirred for an additional 30 minutest 70°C? after which the 5 reaction was cooled to room temperature. The reaction mixture was extracted with dichloromethane (totally 200 ml), after which the red organic layer was dried over MgSC>4, filtered and evaporated under reduced pressure, to yield 4.51 g of a red/brown oil. After scratching the bottom with a spatula the residue turned solid, trying to purify the crude product by washing it with water the product became messy, so immediately
10 the purification was stopped and dried with ether. A sample was taken to analyse the product by NMR, while the rest was immediately reacted with Mn(OAc)a (see complexation).
!H-NMR (400MHz) (CDC13); d (ppm): 1.65 (q-5, propane-A, 2H), 2.40 (t, propane-B, 4H), 3.60 (s, N-CH2-pyr, 8H), 6.95 (t, pyr-H4, 4H), 7.30 (d, pyr-H3, 4H), 7.45 (t, pyr-
15 H5,4H), 8.35 (d, pyr-H6,4H).
To a stirred solution of 4.51 g TPTN (0.0103 mol) in 40 ml methanol is added at room tenipemture (22°C) 2.76 g Mn(OAc)3 (0.0103 mol) . The colour of the reaction turned from orange to dark brown, after the addition the mixture was stirred for 30 minutes at room temperature and filtered. To the filtrate was added at room temperature
20 1.44 g NaC104 (0.0103 mmol) arid the reaction mixture was stirred for another hour, filtered and nitrogen dried, yielding 0.73 g bright brown crystals (8%). "H-NMR (400MHz) (CD3CN); d (ppm): -42.66 (s), -15.43 (s), -4.8 (s, br.), 0-10 (m, br.), 13.8r(s), 45.82 (s), 49.28 (s), 60 (s, br,), 79 (s, br.), 96 (s, br.) W (cm-1): 3426, 1608 (C=C), 1563 (C=N), 1487 , 1430 (C-H), 1090 (C104), 1030,
25 767,623.
UV/Vis (K nm(s, hnol"W): 260 (2.4 xlO4), 290 (sh), 370 (sh), 490 (5.1 xlO2), 530 (sh; 3.4 xlO2); 567 (sh), 715 (1.4 x 102).
Mass spectrum: (ESP+) m/z 782 [TPTN Mn(II)Mn(III) (u-OH) (u-OAc)2 (C104) ESR (CH3CN): The complex is ESR silent supporting the presence of a Mn(in)Mn(IH)
30 species.

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Elemental analysis: found (expected for Mn2C31H38N6O14C12 (MW=899): C 41.14
(41.4), H 4.1 (4.2), N 9.23 (9.34), 0 24.8 (24.9), CI 7.72 (7.9), Mn 12.1 (12.2).
xiv) [Mn2(tpa)2(µ-O)2](PF6)3 (14)
5 Synthesised according to D.K. Towle, C.A. Botsford, DJ. Hodgson, ICA, 141,
167(1988);
xv) [Fe(N4PyXCH3CN)](C1O4)2(15)
Synthesised according to WO-A-9534628; 0
xvi) [Fe(MeN4PyXCH3CN)](C1O4)2 (16)
Synthesised according to EP-A-0909809.
15 Results:

BL: Reference: no catalyst added, only buffer with and without LAS Compound 16 with 10 mM hydrogen peroxide
Table: bleach activity on Tomato Oil stains expressed in AE values obtained for various metal complexes.

WE CLAIM:
1. A process for the manufacture of a bleaching composition adapted to bleach a substrate by the atmospheric oxygen comprising the step of providing a bleach catalysing complex obtained of an organic substrate of formula L and a transition metal such that the bleaching composition obtained thereof upon addition to an aqueous medium provides an aqueous bleaching medium substantially devoid of a peroxygen bleach or a peroxy-based or peroxyl-generating bleach system, wherein L represents a ligand of the general formula (BI):
wherein
g represents zero or an integer from 1 to 6;
r represents an integer from 1 to 6;
s represents zero or an integer from 1 to 6;
Zl and Z2 independently represent a heteroatom or a heterocyclic or heteroaromatic ring, Zl and/or Z2 being optionally substituted by one or more functional groups E as defined below;
Ql and Q2 independently represent a group of the formula:

wherein
10>d+e+f>l; d=0-9; e=0-9; fM)-9;

each Yl is independently selected from -0-, -S-, -SO-, -SO2-, -(G1)N-, -(G1)(G2)N-(wherein G1 and G2 are as defined below), -C(O)-, arylene, alkylene, heteroarylene, -P-and -P(O)-;
if s>l, each -[-Zl(Rl)-(Ql)r-]- group is independently defined;
Rl, R2, R6, R7, R8, R9 independently represent a group selected from hydrogen, hydroxyl, -OR (wherein R= alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl or carbonyl derivative group), -OAr, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups, each of R, Ar, alkyl, alkenyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl and carbonyl derivative groups being optionally substituted by one or more functional groups E, or R6 together with R7 and independently R8 together with R9 represent oxygen;
E is selected from functional groups containing oxygen, sulphur, phosphorus, nitrogen, selenium, halogens, and any electron donating and/or withdrawing groups (preferably E is selected from hydroxy, mono- or polycarboxylate derivatives, aryl, heteroaryl, sulphonate, thiol (-RSH), thioethers (-R-S-R), disulphides (-RSSR), dithiolenes, mono- or polyphosphonates, mono- or polyphosphates, electron donating groups and electron withdrawing groups, and groups of formulae (G1)(G2)N-, (G )(G ) (G3)N-, (G1)(G2)N-C(O)-, G3O- and G3C(O)-, wherein each of G1, G2 and G3 is independently selected from hydrogen, alkyl, electron donating groups and electron withdrawing groups (in addition to any amongst the foregoing));
or one of R1-R9 is a bridging group bound to another moiety of the same general formula;
Tl and T2 independently represent groups R4 and R5, wherein R4 and R5 are as defined for R1-R9, and if g=0 and s>0, Rl together with R4, and/or R2 together with R5, may optionally independently represent =CH-R10, wherein R10 is as defined for Rl-R9, or
Tl and T2 may together (-T2-T1-) represent a covalent bond linkage when s>l and g>0;
if Zl and/or Z2 represent N and Tl and T2 together represent a single bond linkage and Rl and/or R2 are absent, Ql and/or Q2 may independently represent a group of the formula: =CH-[-Yl-]e-CH=,

optionally any two or more of Rl, R2, R6, R7, R8, R9 independently are linked together by a covaient bond;
if Zl and/or Z2 represents O, then Rl and/or R2 do not exist; if Zl and/or Z2 represents S, N, P, B or Si then Rl and/or R2 may be absent; if Zl and/or Z2 represents a heteroatom substituted by a functional group E then Rl and/or R2 and/or R4 and/or R5 may be absent.
2. A method as claimed in claim 1, wherein Zl and Z2 independently represent an optionally substituted heteroatom selected from N, P, O, S, B and Si or an optionally substituted heterocyclic ring or an optionally substituted heteroaromatic ring selected from pyridine, pyrrolidines, pyrazine, pyramidine, pyrazole, pyrrole, imidazole, benzimidazole, quinoleine, isoquinoline, carbazole, indole, isoindole, furane, thiophene, oxazole and thiazole.
3. A method as claimed in anyone of claims 1 or 2, wherein R1-R9 are independently selected from -H, hydroxy-C0-C20-alkyl, halo-C0-C20-alkyl, nitroso, formyl-C0-C20-alkyl, carboxyl-.C0-C20-alkyl and esters and salts thereof, carbamoyl-Co-C20-alkyl, sulpho-C0-C20-alkyl and esters and salts thereof, sulphamoyl-C0-C20-alkyl, amino-C0-C20-alkyl, aryl-C0-C20-alkyl, heteroaryl-C0-C20-alkyl, C0-C20-alkyl, alkoxy-C0-C8-alkyl, carbonyl-C0-C6-alkoxy, and aryl-C0-C6 alkyl and Co-C2o-alkylamide;
or one of R1-R9 is a bridging group -Cn(Rll)(R12)-(D)p-Cm(Rll)(R12)- bound to another moiety of the same general formula, wherein p is zero or one, D is selected from a heteroatom or a heteroatom-containing group, or is part of an aromatic or saturated homonuclear and heteronuclear ring, n" is an integer from 1 to 4, m" is an integer from 1 to 4, with the proviso that n"+m" 4. A method as claimed in any one of claims 1 to 2, wherein Tl and T2 together
form a single bond linkage and s>l, as claimed in claimgeneral formula (BII):

wherein Z3 independently represents a group as defined for Zl or Z2; R3 independently represents a group as defined for R1-R9; Q3 independently represents a group as defined for Ql, Q2; h represents zero or an integer from 1 to 6; and s"=s-l.
5. A method as claimed in claim 4, wherein in general formula (BII) used s"=l, 2 or 3; r=g=h=l; d=2 or 3; e=f=0; R6=R7=H.
6. A method as claimed in claim 5, wherein the ligand used has a general formula selected from:

7. A method as claimed in claim 6, wherein the ligand used has a general formula selected from:

8. A method as claimed in claim 7, wherein Rl, R2, R3 and R4 are independently selected from -H, alkyl, heteroaryl, or represents a bridging group bound to another moiety of the same general formula with the bridging group being alkylene or hydroxy-alkylene or a heteroaryl-containing bridge.
9. A method as claimed in claim 8, wherein Rl, R2, R3 and R4 are independently selected from -H, methyl, ethyl, isopropyl, nitrogen-containing heteroaryl, or a bridging group bound to another moiety of the same general formula with the bridging group being alkylene or hydroxy-alkylene.
10. A method as claimed in any of claims 5 to 9, wherein in the complex [MaLkXn]Ym used:
M= Mn(II)-(IV), Cu(I)-(III), Fe(II)-(III), Co(II)-(HI);
X= CH3CN, OH2, C1, Br, OCN", N3-, SCN", Off , O2-, PO43", C6H5BO22-, RCOO";
Y= C104 BPV, Br", C1 , [FeCl4] PF6", NO3"
a= 1, 2, 3, 4;
n= 0, 1, 2, 3, 4, 5, 6,7, 8, 9;
m= 1, 2, 3, 4; and
k= 1, 2, 4.
11. A method as claimed in claim 4, wherein in general formula (BII) used s"=2; r=g=h=l; d=f=0; e=l; and each Yl is independently alkylene or heteroarylene.

12. A method as claimed in claim 11, wherein the ligand used has the general
formula:

wherein
A1, A2, A3, A4 are independently selected from C1-9-alkylene or heteroarylene groups; and
N1 and N2 independently represent a hetero atom or a heteroarylene group.
13. A method as claimed in claim 12, wherein
N1 represents an aliphatic nitrogen;
N2 represents a heteroarylene group;
Rl, R2, R3, R4 each independently represent -H, alkyl, aryl or heteroaryl; and
Ai, A2, A3, A4 each represent -CH2-.
14. A method as claimed in claim 13, wherein the ligand used has the general
formula:

wherein Rl, R2 each independently represent -H, alkyl, aryl or heteroaryl.
15. A method as claimed in anyone of claims 11 to 14, wherein in the complex [MaLkXn] Ym used :

M= Fe(II)-(III), Mn(II)-(IV), Cu(II), Co(II)-(III);
X= CH3CN, 0H2, C1", Br", OCN", N3 SCN, OH" , O2-, P043 C6H5BO22-, RCOO";
Y= C1O4, BPh4 Br", CI", [FeCl4] PF6 NO3";
a= 1, 2, 3, 4;
n= 0, 1, 2, 3, 4, 5, 6,7, 8, 9;
m= 1, 2, 3, 4; and
k= 1, 2, 4.
16. A method as claimed in claim 14, wherein in general formula (BII) used s"=2 and
r=g=h=l, as claimed in the general formula:

17. A method as claimed in claim 16, wherein Zl=Z2=Z3=Z4=a heteroaromatic ring; e=f=0; d=l; and R7 is absent.
18. A method as claimed in claim 16, wherein Z1-Z4 each represent N; R1-R4 are absent; both Ql and Q3 represent =CH—[—Yl— ]e—CH= ; and both Q2 and Q4 represent -CH2-[-Yl-]m-CH2-.
19. A method as claimed in claim 18, wherein the ligand used has the general formula:

wherein A represents optionally substituted alkylene optionally interrupted by a heteroatom; and n is zero or an integer from 1 to 5.
20. A method as claimed in claim 19, wherein R1-R6 represent hydrogen, n=l and A= -CH2-, -CHOH-, -CH2N(R)CH2- or -CH2CH2N(R)CH2CH2- wherein R represents hydrogen or alkyl.
21. A method as claimed in claim 20, wherein A= -CH2-, -CHOH- or -CH2CH2NHCH2CH2-.
22. A method as claimed in anyone of claims 13 to 21, wherein in the complex [MaLkXn]Ymused :
M= Mn(II)-(IV), Co(II)-(III), Fe(II)-(III);
X= CH3CN, OH2, C1", Br", OCN", N3", SCN", OFT , O2", PO43- C6H5BO22
RCOO";
Y= C1O4", BPh4", Br -, C1", [FeCl4] PF6", NO3"
a= 1, 2, 3, 4;
n= 0,1, 2, 3, 4, 5, 6,7, 8, 9; m= 1, 2, 3, 4; and k= 1, 2, 4.

23. A method as claimed in anyone of claims 1 to 3, wherein Tl and T2
independently represent groups R4, R5 as defined for R1-R9, as claimed in the general
formula (BIII):

24. A method as claimed in claim 23, wherein in general formula (BIII) used, s=l;
r=l; g=0; d=f=l; e=l-4; Yl= -CH2-; and Rl together with R4, and/or R2 together with
R5, independently represent =GH-R10, wherein R10 is as defined for R1-R9.
25. A method as claimed in claim 24, wherein R2 together with R5 represents =CH-
R10.
26. A method as claimed in claim 24 or claim 25, wherein the ligand used is selected
from:

27. A method as claimed in claim 26, wherein the ligand used is selected from:

wherein Rland R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, heteroaryl-C0-C20-alkyls, alkylaryl, aminoalkyl, alkoxy.

28. A method as claimed in claim 27, wherein Rl and R2 are selected from optionally substituted phenols, heteroaryl-C0-C20-alkyls, R3 and R4 are selected from -H, alkyl, aryl, optionally substituted phenols, nitrogen-heteroaryl-Co-C2-alkyls.
29. A method as claimed in anyone of claims 37 to 41 wherein in the complex [MaLkXn]Ymused:
M= Mn(II)-(IV), Co(II)-(III), Fe(II)-(III);
X= CH3CN, OH2, C1", Br", OCN", N3", SCN", OH , O2", PO43", C6H5BO22", RCOCr;
Y= C1O4", BPh4", Br", C1", [FeCl4]", PF6 NO3";
a= 1, 2, 3, 4;
n= 0,1,2,3,4,5,6,7,8,9;
m= 1, 2, 3, 4; and
k= 1, 2, 4.
30. A method as claimed in claim 23, wherein in general formula (Bill) used, s=l; r=l; g=0; d=f=l; e=l-4; Yl= -C(R")(R"X wherein R" and R" are independently as denned for R1-R9.
31. A method as claimed in claim 30, wherein the ligand used has the general formula:

32. A method as claimed in claim 31, wherein Rl, R2, R3, R4, R5 are -H or C0-C20-alkyl, n=0 or 1, R6 is -H, alkyl, -OH or -SH, and R7, R8, R9, R10 are each independently selected from -H, Co-C20-a!kyl, heteroaryl-C0-C20-alkyl, alkoxy-C0-C8-alkyl and amino- CcrC20-alkyl.
33. A method as claimed in anyone of claims 30 to 32, wherein in the complex [MaLkXn]Ym used:

M= Mn(II)-(IV), Fe(II)-(III), Cu(II), Co(H)-(III);

X= CH3CN, OH2, C1, Br", OCN", N3, SCN Off , O2- , PO4", C6H5BO2 ,
RCOO
3
Y= C1O4", BPh4", Br", C1", [FeCl4]-, PF6", NO3";
a= 1, 2, 3, 4;
n= 0,1,2,3,4;
m= 0, 1, 2, 3, 4, 5, 6, 7, 8; and
k= 1, 2, 3, 4.
34. A method as claimed in claim 23, wherein in general formula (BIII) used, s=0; g=l;d=e=0;f=l-4.
35. A method as claimed in claim 34, wherein the ligand used has the general formula:

wherein Rl, R2, R3 are as defined for R2, R4, R5.
36. A method as claimed in claim 35, with the proviso that none of Rl to R3 represents hydrogen.
37. A method as claimed in claim 35 or claim 36, wherein the ligand used has the general formula:

38. A method as claimed in anyone of claims 34 to 37, wherein in the complex [MaLkXn] Ym used :
M= Mn(II)-(IV), Fe(II)-(III), Cu(II), Co(II)-(III);
X= CH3CN, OH2, CI", Br", OCN, N3 SCN, OH" , O2 PO43", C6H5BO22-, RCOO";
Y= C1O4 BPh4", Br", C1", [FeCl4]", PF6 NO3";
a= 1, 2, 3, 4;
n= 0,1,2,3,4;
m= 0, 1, 2, 3, 4, 5, 6, 7, 8; and
k= 1, 2, 3, 4.
39. A method as claimed in anyone of claims 1 to 3, wherein L represents a pentadentate ligand of the general formula (B):

wherein
each R1, R2 independently represents -R4-R5,
R3 represents hydrogen, optionally substituted alkyl, aryl or arylalkyl, or -R4-R5,
each R4 independently represents a single bond or optionally substituted alkylene, alkenylene, oxyalkylene, aminoalkylene, alkylene ether, carboxylic ester or carboxylic amide, and
each R5 independently represents an optionally N-substituted aminoalkyl group or an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl.
40. A method as claimed in claim 39, with the proviso that R3 does not represent hydrogen.

41. A method as claimed in anyone of claims 1 to 3, wherein L represents a
pentadentate or hexadentate ligand of the general formula (C):
R1R1N-W-NR1R2
wherein
each R1 independently represents -R3-V, in which R3 represents optionally substituted alkylene, alkenylene, oxyalkylene, arninoalkylene or alkylene ether, and V represents an optionally substituted heteroaryl group selected from pyridinyl, pyrazinyl, pyrazolyl, pyrrolyl, imidazolyl, benzimidazolyl, pyrimidinyl, triazolyl and thiazolyl;
W represents an optionally substituted alkylene bridging group selected from -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2-C6H4-CH2-, -CH2-C6H10-CH2-, and -CH2-C10H6-CH2-; and
R2 represents a group selected from R1, and alkyl, aryl and arylalkyl groups optionally substituted with a substituent selected from hydroxy, alkoxy, phenoxy, carboxylate, carboxamide, carboxylic ester, sulphonate, amine, alkylamine and N+(R4 )3, wherein R4 is selected from hydrogen, alkanyl, alkenyl, arylalkanyl, arylalkenyl, oxyalkanyl, oxyalkenyl, aminoalkanyl, aminoalkenyl, alkanyl ether and alkenyl ether.
42. A method as claimed in anyone of claims 1 to 3, wherein L represents a
macrocyclic ligand of formula (E):

wherein
Z1 and Z2 are independently selected from monocyclic or polycyclic aromatic ring structures optionally containing one or more heteroatoms, each aromatic ring structure being substituted by one or more substituents;
Yl and Y2 are independently selected from C, N, O, Si, P and S atoms;

A1 and A2 are independently selected from hydrogen, alkyl, alkenyl and cycloalkyl (each of alkyl, alkenyl and cycloalkyl) being optionally substituted by one or more groups selected from hydroxy, aryl, heteroaryl, sulphonate, phosphate, electron donating groups and electron withdrawing groups, and groups of formulae (G1)(G2)N-, G3OC(O)-, G3O-and G3C(O)-, wherein each of G1, G2 and G3 is independently selected from hydrogen and alkyl, and electron donating and/or withdrawing groups (in addition to any amongst the foregoing);
i and j are selected from 0, 1 and 2 to complete the valency of the groups Y1 and
each of Q -Q is independently selected from groups of formula

wherein 10>a+b+c+d>2;
each Y3 is independently selected from -0-, -S-, -SO-, -S02-, -(G1)(G2)N-, -(G!)N-
(wherein G1 and G2 are as hereinbefore defined), -C(O)-, aryl, heteroaryl, -P- and -P(O)-;
each of A3-A6 is independently selected from the groups hereinbefore defined for A1 and
A2; and
wherein any two or more of A1-A6 together form a bridging group, provided that if A1
and A2 are linked without simultaneous Unking also to any of A3-A6, then the bridging
group linking A1 and A2 must contain at least one carbonyl group.
43. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a pH value in the range from pH 6 to 11.
44. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a pH value in the range from pH 8 to 10.

45. A method as claimed in any preceding claims wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a medium substantially devoid of a transition metal sequestrant.
46. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a medium further comprising a surfactant.
47. A method as claimed in any preceding claims, wherein the bleaching composition is obtained such as to provide upon addition to an aqueous medium a medium comprising a builder.
48. A method as claimed in any preceding claims, wherein the organic substance comprises a preformed complex of a ligand and a transition metal.
49. A method as claimed in any one of claims 1 to 47, wherein the organic substance used comprises a free ligand that complexes with a transition metal present in the water.
Dated this 1st day of March 2001
ANJAN SEN Of S. MAJUMDAR & CO. Applicants" Agent

Documents:

in-pct-2001-00238-mum-claims(granted)-(11-12-2003).doc

in-pct-2001-00238-mum-claims(granted)-(11-12-2003).pdf

IN-PCT-2001-00238-MUM-CORRESPONDENCE(8-2-2012).pdf

in-pct-2001-00238-mum-correspondence(ipo)-(30-12-2004).pdf

in-pct-2001-00238-mum-correspondence1(1-3-2001).pdf

in-pct-2001-00238-mum-correspondence2(12-11-2007).pdf

in-pct-2001-00238-mum-form 13(17-10-2007).pdf

in-pct-2001-00238-mum-form 19(23-6-2003).pdf

in-pct-2001-00238-mum-form 1a(12-1-2004).pdf

in-pct-2001-00238-mum-form 2(granted)-(11-12-2003).doc

in-pct-2001-00238-mum-form 2(granted)-(11-12-2003).pdf

in-pct-2001-00238-mum-form 3(1-3-2001).pdf

in-pct-2001-00238-mum-form 5(1-3-2001).pdf

in-pct-2001-00238-mum-form-pct-isa-210-(1-3-2001).pdf

in-pct-2001-00238-mum-power of attorney(1-7-2002).pdf

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Patent Number

211675

Indian Patent Application Number

IN/PCT/2001/00238/MUM

PG Journal Number

04/2008

Publication Date

25-Jan-2008

Grant Date

07-Nov-2007

Date of Filing

01-Mar-2001

Name of Patentee

HINDUSTAN UNILEVER LIMITED

Applicant Address

HINDUSTAN LEVER HOUSE, 165/166, BACKBAY RECLAMATION, MUMBAI- 400 020

Inventors:

#	Inventor's Name	Inventor's Address
1	TETARD,DAVID	UNILEVER R&D PORT SUNLIGHT,QUARRY ROAD EAST,BEBINGTON,WIRRAL,MERSEYSIDE,CH63 3JW
2	THORNTHWAITE,DAVID WILLIAM	UNILEVER R&D PORT SUNLIGHT,QUARRY ROAD EAST,BEBINGTON,WIRRAL,MERSEYSIDE,CH63 3JW
3	TIWARI,LAXMIKANT	UNILEVER R&D PORT SUNLIGHT,QUARRY ROAD EAST,BEBINGTON,WIRRAL,MERSEYSIDE,CH63 3JW
4	THIJSSEN,ROB	UNILEVER R&D VLAARDINGEN,OLIVER VAN NOORTLAAN 120,3133 AT VLARRDINGEN
5	TWISKER,ROBIN STEFAN	UNILEVER R&D VLAARDINGEN,OLIVER VAN NOORTLAAN 120,3133 AT VLARRDINGEN
6	VEERMAN,SIMON MARINUS	UNILEVER R&D VLAARDINGEN,OLIVER VAN NOORTLAAN 120,3133 AT VLARRDINGEN
7	VAN DER VOET GERRIT	UNILEVER R&D VLAARDINGEN,OLIVER VAN NOORTLAAN 120,3133 AT VLARRDINGEN
8	APPEL ADRIANUS CORNELIS MARIA	UNILEVER R&D VLAARDINGEN, OLIVIER VAN NOORTLANN 120, 3133 AT VLAARDINGEN
9	HAGE RONALD	UNILEVER R&D VLAARDINGEN, OLIVIER VAN NOORTLAAN 120, 3133 AT VLAARDINGEN,
10	CARINA RICCARDO FILIPPO	1 RUE J PASQUIER, 1203 GENEVE,
11	DELROISSE MICHEL GILBERT JOSE	UNILEVER R&D VLAARDINGEN, OLIVIER VAN NOORTLANN 120, 3133 AT VLAARDINGEN
12	FERINGA BERNARD LUCAS	HENRI DUNANTWEG 8, 9765 EP PATERSWOLDE,
13	GIRERD JEAN-JACQUES	2 ALLEE ELIZABETH DE FEYDEAU, 91190 GIF-SUR-YVETTE,
14	KALMEIJER ROBERTS EVERARDUS	UNILEVER R&D VLAARDINGEN, OLIVIER VAN NOORTLAAN 120, 3133 AT VLAARDINGEN,
15	MARTENS CONSTANTINUS FRANCISCUS	UNILEVER R&D VLAARDINGEN, OLIVIER VAN NOORTLAAN 120, 3133 AT VLAARDINGEN,
16	PEELEN JACOBUS CAROLINA JOHANNNES	UNILEVER R&D VLAARDINGEN, OLIVIER VAN NOORTLAAN 120, 3133 AT VLAARDINGEN,
17	QUE JR LAWRENCE	1784 SARGENT AVENUE,ST PAUL,MINNESOTA 55105
18	SWARTHOFF,TON	UNILEVER R&D VLAARDINGEN,OLIVER VAN NOORTLAAN 120,3133 AT VLARRDINGEN

PCT International Classification Number

C11D 3/395

PCT International Application Number

PCT/GB99/02876

PCT International Filing date

1999-09-01

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	9819046.5	1998-09-01	U.K.
2	9907714.1	1999-04-01	U.K.
3	9906474.3	1999-03-19	U.K.