Title of Invention

A RUTHENIUM COMPLEX WITH A CHIRAL FERROCENYL-DIPHOSPHINE LIGAND FOR HOMOGENEOUS CATALYSIS AND A PROCESS FOR PREPARING THE SAME

Abstract

The invention relates to ruthenium complexes with a chiral ferrocenyldiphosphine ligand, wherein the ruthenium has the oxidation state (+II) and the chiral ferrocenyldiphosphine ligand has bidentate P-P coordination to the ruthenium. The ruthenium complexes are cyclic and with the ferrocenyldiphosphine ligand have an at least eight-membered ring. The ferrocenyldiphosphine ligands are selected from the group consisting of Taniaphos, Taniaphos-OH and Walphos ligands. A process for preparing the Ru complexes is described. The Ru complexes are used as catalysts for homogeneous asymmetric catalysis for preparing organic compounds.

Full Text

Ruthenium complexes with (F-P)-coordinated ferrocenyldiphosphine ligands, process £or preparing them, and their use in homogeneous catalysis Description The present invention relates to ruthenium complexes for homogeneous catalysis. In particular, the invention relates to ferrocene-containing, P-P-coordinated ruthenium complexes with chiral diphosphine ligands (known as ferrocenyldiphosphine ligands) and a process for preparing them. The invention further relates to the use of these complexes as catalysts for homogeneous catalytic hydrogenation. Chiral ferrocenyldiphosphines have proven to be valuable ligands for catalytically active metal complexes which are used in homogeneous catalysis for the enantioselective hydrogenation of organic conqpounds. Fields of use are the preparation of intermediates or active compounds, for example pharmaceuticals, pesticides, flavors or fragrances. Among the diphosphines having a ferrocene framework, l-sec-phosphino-2-(2'-sec-phosphino-1-benzyl)- ferrocenes, for excunple, have proven to be valuable ligands for noble metal complexes for the enantioselective hydrogenation of organic compounds. Ligands of this type are referred to by the name "Taniaphos" and are described in WO 00/37478. Further examples of diphosphines having a ferrocene framework are 1-(a-sec-phosphinoalkyl)-2-(sec-phosphinoaryl)- ferrocenes which are disclosed in WO 02/02578 (trivial neune "Walphos") . In enantioselective hydrogenation, these diphosphine ligands are used together with suitable noble metal complexes. The reaction of asymmetric ferrocenyl- diphosphine ligands with organometallic Ru con^ovinds leads to mixtures of complexes which have monodentate coordination of the P atoms of the phosphine ligand, cf. equ. (1): Equation (1) : According to equ. (1) , an isomer mixture of monodentate, P-coordinated Ru conplexes in which in each case, only one of the P atoms of the ferrocenyldiphosphine ligcuid is bound to the ruthenium is present. The two isomers in equation (1) can be distinsruished, for example, by means of ^^P-NMR spectroscopy. Simultaneous coordination of both P atoms of the ferrocenyldiphosphine ligand in a ruthenium coirplex (hereinafter referred to as "bidentate" coordination or "P-P coordination") has hitherto not been observed. Organometallic Ru conpounds used in these hydro- genations are, for example, [Ru(COD)y2]x- [Ru(NBD)Y2]x/ [Ru(aromatic)Y2]x or [Ru(COD) (2-methylallyl) 2] (where X = 2; Y = halide, COD = 1,5-cyclooctadiene, NBD = norbornadiene, aromatic = for example, p-cumene or another benzene derivative). EP 1622920B1 discloses transition metal complexes with ferrocenyldiphosphine ligands. Complexes having specific P-P coordination of the phosphine ligands are not described, and in addition the diphosphine ligands disclosed have phosphine groups which are located on different ferrocene rings of the ligand system. Although WO 00/37478 describes transition metal complexes which contain a metal atom of transition group 7 or 8 and in which both P atoms of the ferrocenyldiphosphine ligand are simultaneously coordinated to the central atom, the complexes are neither isolated nor characterized. No process for preparing them is described; rather, the complexes are generated shortly before use by combining the ligands and the appropriate treinsition metal salts in the reaction solvent ("in situ") . These in-si tu processes are prior art. Thus, ferrocenyldiphosphine ligands are reacted with ruthenitim complexes in an in-situ procedure; cf. Angewandte Chemie 1999, 111, No. 21, 3397-3400. Here, [Ru(COD) (C4H7)2]HBr (COD = cycloocta-1,5-diene, C4H7 = 2-(T|^-)methylallyl) is used as Ru complex and 3-keto esters of the type R-C0-CH2-CO-OEt are hydrogenated in ethcmol at 50°C under 50 bar of hydrogen. The seime Ru starting coitpound is used in Tetrahedron Asymmetry 1^ (2004) 91-102 and the catalyst is prepared in situ. Adv, Synth. Catal. 2003, 345, 160-164 describes phenyl- ferrocenylethyldiphosphine ligands of the "Walphos" type. Dimeric [RUI2 (p-cvimene) ]2 is used as Ru-containing catalyst precursor in the hydrogenation and the catalyst is formed in situ. However, no studies on the structure of the metal complexes generated in situ have hitherto been carried out; the corresponding con^lexes were not isolated but used directly in the reaction mixture for homogeneous catalysis, in particular for catalytic hydrogenation. Disadvantages of the catalytic hydrogenation processes which have been described up to now and the catalysts used therein are, in particular, the low enantio- selectivities and a high consumption of noble metal catalysts, i.e. a low substrate/catalyst (S/C) ratio, and long hydrogenation times. It was therefore an object of the present invention to provide inproved catalysts for homogeneous, asymmetric hydrogenation. This object is achieved by provision of the rutheniiom complexes of the types (A) and (B) as claimed in claim 1 of the invention. Furthermore, a process for preparing the complexes of the invention is disclosed in claim 11. Preferred embodiments are described in the subordinate claims dependent thereon. The present invention describes ruthenium complexes with a chiral ferrocenyldiphosphine ligand for homogeneous catalysis, wherein the ruthenium has the oxidation state (+11) and the ferrocenyldiphosphine ligands have bidentate P-P coordination to the Ru. The ruthenium complexes are cyclic and with the ferrocenyldiphosphine ligaund have an at least eight- membered ring. The ferrocenyldiphosphine ligands are, for example, selected from the group consisting of "Taniaphos" and "Walphos' ligands, but are not restricted to these ligands. The present invention further provides a process for preparing the ruthenium complexes of the invention, in which specific Ru starting compounds are reacted with a chiral ferrocenyldiphosphine ligand. In the search for well-defined Ru complexes with ferrocenyldiphosphine ligands, it has surprisingly been found that simultaneous coordination of both P atoms of the ferrocenyldiphosphine ligands to a central Ru atom can be achieved under particular conditions. This gives cyclic Ru complexes which have an at least eight- membered ring in their structure (number of ring members r > 8) . The effect of P-P coordination is obtained by use of specific ferrocenyldiphosphine ligands which have at least seven ring-forming atoms in their structure and are therefore sterically capable of forming an at least eight-membered ring with the central Ru atom. The phosphino groups are preferably located on one (i.e. on the Scune) cyclopentadienyl ring of the ferrocene molecule. Example of suitable ferrocenyldiphosphine ligands are ligands of the Taniaphos type and their derivatives, for exainple Taniaphos-OH or Taniaphos-OMe, etc. However, it is also possible to use ligands of the "Walphos" type. Examples of suitable ferrocenyl- diphosphine ligands for preparing the Ru complexes of the invention are: (S) -l-diphenylphosphino-2- [ (R) -a- (N,N-dimethyl- amino) -o- (diphenylphosphinophenyl) methyl] ferrocene (= Taniaphos TOOl-1) (R) -l-diphenylphosphino-2- [ (S) -a- {N,N-dimethyl- amino) -o- (diphenylphosphinophenyl)methyl] ferrocene (= Taniaphos TOOl-2) (S) -l-dicyclohexylphosphino-2- [ (R) -a- (N, N-di- methylamino) -o- (dicyclohexylphosphinophenyl) - methyl]ferrocene (= Taniaphos T002-1) (R)~l-dicyclohexylphosphino-2-[(S)-a-(N,N-di- methylamino) -o- (dicyclohexylphosphinophenyl) - methyl]ferrocene {= Taniaphos T002-2); (S)-l-diphenylphosphino-2-[a-(S)-hydroxy-(o-di- phenylphosphinophenyl)methyl]ferrocene ("Taniaphos OH"); and derivatives of this type; (S) -l-diphenylphosphino-2- [a- (S) -methoxy (o-di- phenylphosphinopheny 1 )methyl]ferrocene ("Taniaphos OMe'); cind derivatives of this type (cf. WO 2003/076451); (R) -1-[(R)-2- (2'-diphenylphosphinophenyl)ferro- cenyl]ethyIdi(bis-3,5-trifluoromethylphenyl)- phosphine {Walphos WOOl-1); (S) -l-[ (S)-2- (2'-diphenylphosphinophenyl)ferro- cenyl]ethyldi(bis-3,5-trifluoromethylphenyl)- phosphine (Walphos WOOl-2); (R)-1-[(R)-2-(2'-diphenylphosphinophenyl)ferro- cenyl]ethyldiphenylphosphine (Walphos WO02-1) ; (S)-l-[(S)-2-(2'-diphenylphosphinophenyl)ferro- cenyl]ethyldiphenylphosphine (Walphos W002-2); (R)-l-[(R)-2-{2'-diphenylphosphinophenyl)ferro- cenyl]ethyldicyclohexylphosphine (Walphos W003-1); (S)-1-[(S)-2-(2'-diphenylphosphinophenyl)ferro- cenyllethyldicyclohexylphosphine (Walphos W003-1); (R) -1- [ (R) -2- (2'-di(3,5-dimethyl-4-methoxyphenyl)- phosphinophenyl)ferrocenyl]ethyldi(bis-3,5-tri- fluoromethyl)phenyl)phosphine (walphos W005-1) ; (S)-1-[(S)-2-(2'-di(3,5-dimethyl-4-methoxyphenyl)- phosphinophenyl)ferrocenyl]ethyldi(bis-3,5-tri- fluoromethylphenyl)phosphine (Walphos W005-2); (R)-1-[(R)-2-(2'-diphenylphosphinophenyl)ferro- cenyl]ethyldi(3,5-xylyl)phosphine (Walphos W006- 1); (S)-1-[(S)-2-(2'-diphenylphosphinophenyl)ferro- cenyljethyldi (3, 5-xylyl)phosphine (Walphos W006- 2); (R) -1- [ (R) -2- (2 ' -dicyclohexylphosphinophenyl) - ferrocenyl]ethyldi(3, 5-trifluoromethyl)phenyl) - phosphine (Walphos W008-1) ; (S) -1- t (S) -2- (2 ' -dicyclohexylphosphinophenyl) - f errocenyl ] ethyldi (3, 5-trif luoromethyl) phenyl) - phosphine {Walphos W008-2). These chiral ferrocenyldiphosphine ligands are in most cases commercially available. Use of these ligands in the preparative process of the invention gives cyclic Ru coitplexes which have an eight-meihbered ring in their structure. However, other chiral ferrocenyldiphosphine ligands are also suitable as long as they allow formation of an at least eight-membered ring (number of ring members r > 8). In the present preparative process, the effect of P-P coordination is achieved by use of specific Ru starting compounds which are present in the oxidation state (+11) and have at least two neutral 2-electron donor ligands Ld- They have the following general formula where Ru is in the oxidation state +11, n is an integer equal to or greater than 3, Lo is an neutral ligand, Z is at least one n-bonded organic ligand and E' is the anion of an oxo acid or complex acid. The at least three neutral ligands Ld generally belong to the class of 2-electron donor ligands such as secondary or tertiary phosphines or N-heterocyclic carbene ligands (knovm as NHC ligands). The ligands Ld are preferably solvent ligands which are bound to the central Ru atom. At least two of these ligands are replaced in the reaction by a chiral diphosphine ligand. Exanqples of suitable ligands Ld are ligands from the group consisting of alcohols, ethers, amines, acid eunides, lactams eind sulfones; for example acetonitrile (CH3CN). diethyl ether (DEE), water (H2O) or acetone. It is also possible to use cyclic ligands such as tetrahydrofuran (THF), dioxane, pyridine, imidazole or thiophene. Mixed systems having different types of ligands, for example ones containing phosphine ligands and/or carbene ligands and/or solvent ligands, are also possible. Furthermore, the Ru starting compound has at least one n-bonded organic ligand Z. Z encompasses substituted or unsubstituted cyclic or open-chain dienyl ligands in general, for example substituted or unsubstituted pentadienyl or heptadienyl ligands. For clarification, such dienyl ligands are, when bonded to the Ru, negatively charged, i.e. anionic. Preference is given to using 2,4-dimethylpentadiene, 2,3,4-trimethylpentadiene, cycloheptadiene, cycloocta- diene, norbornadiene, etc. The ligeuids Z can also be present in the protonated state and have protons in an "agostic interaction*. Most preferably, for Z, one negatively charged open- / chain dienyl ligand, for example 2,4-dimethyl- pentadienyl- or 2,3,4-trimethylpentadienyl- is employed. The Ru starting compound is present as cation having a single positive charge emd has, as further constituent E", the anion of an oxo acid or complex acid as counterion. Exaunples of E" are HSO4', CF3SO3', C104', BF4", B(aryl)4', SbF6' and PF6'. Examples of suitable Ru starting compounds are [Ru(2,4-dimethylpentadienyl) (CH3CN)3]*BF4' or [Ru(2,4- dimethylpentadienyl) (acetone) 3] *BF4*. The Ru starting compound can be prepared in various process steps from known Ru precursor compounds by reaction with the appropriate ligand LD, and isolated. The Ru precursor conpound can be protonated before reaction with the neutral ligand Ld in order to achieve improved ligand replacement by Ld- As Ru precursors, it is possible to use the compounds mentioned above, e.g. bis (?5-(2,4-dimethylpenta- dienyDRu, [Ru{COD)Cl2]2, [Ru(norbomadiene)Cl2]2, [Ru(p-cumene)l2]2 or [Ru{COD)(2-methylallyl)2]. These Ru compounds are commercially available. The preparation procedures for the Ru starting compound have to be adjusted depending on the precursor compound used. A preferred Ru precursor conprises negatively charged Z ligands, such as, for example, bis diS-(2,4-dimethyl- pentadienyDRu. The preparation of the Ru starting compoxmd typically proceeds in two steps: Step A (protonation): [Zi-Ru] + H* E => [Zz-Ru-H ]+ + E' step B (ligand exchange) : [Z2-Ru-H]+E- + dLd => [Z-Ru (LD)n r E" + Z-H It has been found that reaction of the Ru starting compounds with the appropriate chiral ferrocenyl- diphosphine ligands (hereinafter represented as P(l)-P(2) for short) gives the Ru complexes of the invention. The formation of the ferrocenyldiphosphine conplex then occurs in step C. The preparative process of the invention is shown in general form in equ. (2): The reaction of equ. (2) gives the novel Ru complexes of type (A) . To prepare the Ru complexes of type (A) , the ferrocenyldiphosphine ligands are reacted with the above-described Ru starting compound, resulting in at least two of the ligands Ld being replaced by the chiral diphosphine ligands in the reaction. If the Ru starting compoiind has more than two ligands Ld, the remaining ligands Ld remain coordinated to the ruthenium. They can be replaced or eliminated in a subsequent step. The preparation of the Ru complexes is preferably carried out vmder a protective gas atmosphere using the Schlenk technique and oxygen-free solvents. The ferrocenyldiphosphine ligands are typically reacted with the Ru starting compound in a suitable solvent at temperatures in the range from 20 to 80°C, preferably in the range from 20 to 60°C and particularly preferably at room temperature (25°C) , while stirring. Suitable solvents are chlorinated hydrocarbons such as chloroform, methylene chloride, trichloroethane or dichloroethane. The reaction times range from 1 hour to 10 hours. It can be advantageous to use the ligand in a small excess in the preparation of the Ru complexes. The excess can be in the range from 1 to 10 mol% (based on the Ru starting compound) . The subsequent isolation, washing and purification steps are well known to those skilled in the art. To remove solvent residues, the product is dried under reduced pressure. In a further embodiment, the present invention encompases Ru complexes of type (B) . These complexes bear no net charge and have a negatively charged ligand Lz in addition to the P-P-coordinated ferrocenyl- diphosphine ligand, the n-bonded organic ligand Z and, if appropriate, the ligcuid Ld- This ligand Lz can be introduced by replacement of one of the ligands Ld by a halide ion (fluoride, chloride, bromide or iodide) or a pseudohalide ion (e.g. CN", SCN', cyanate, isocyanate, etc.). The Ru complex of type (B) is preferably prepared from the complex of type (A) by subsequent ligand exchange, for example by replacement of an acetonitrile molecule by iodide (cf. example 2): Step D (replacement of the ligand Ld by negatively charged ligands Lz) according to equ. (3). To carry out step D, the cationic Ru complex (type A) is dissolved in a dipolar, aprotic solvent, for example acetone or THF, and reacted with ligand Lz at temperatures in the range from 20 to 50°C. The product generally precipitates and can be separated off. The novel Ru complexes of type (A) where, in each case, Ru is in the oxidation state +11, n is an integer equal to or greater than 3, Ld is an neutral ligand, Z is at least one n-bonded organic ligand, E" is an anion of an oxo acid or complex acid and Lz is at least one anionic ligand and the ferrocenyldiphosphine ligand P(l)-P(2) has bidentate P-P coordination, are effective homogeneous catalysts for the asymmetric hydrogenation of prochiral organic confounds. They are therefore used as catalysts for homogeneous asymmetric catalysis, for exanple for the enantio- selective hydrogenation of multiple bonds. For the purposes of the present invention, multiple bonds are double bonds between a carbon atom and a further carbon atom (C=C) or oxygen atom (C=0) or nitrogen atom (C=N). Furthermore, the ruthenium complexes of the invention can also be used as catalysts for other asymmetric reactions. These include C-C, C-0, C-N, C-P, C-Si, C-B or C-halogen bond formation reactions. Examples are asynmietric cyclization reactions, asymmetric oligo- merizations and asymmetric polymerization reactions. The novel Ru complexes of type (A) and (B) are used as defined compounds and display, for example, very good catalytic properties in hydrogenation. In comparison, Ru complexes which only have single, monodentate coordination of the P atoms of the ferrocenyldiphosphine ligands or Ru compounds which are used together with the ferrocenyldiphosphine ligands in the in-situ process display poorer catalytic properties. The following examples illustrate the invention. EXAMPLES Example 1: Preparation of (t]5-2, 4-djjBethylpazitadienyl) - (CH3CN) - (Taniaphos T001-l}rutheniua(II) tetrafluoroborate a) Preparation of (n4-2,4-dimethylpentadiene-'n2-C,H)- (115-2, 4-dimethylpentadienyl) ruthenium tetrafluoro- borate In a 100 ml Schlenk tube provided with a magnetic stirrer, 1.1 g (3.77 mmol) of bis (Ti5-2, 4-dimethylpenta- dienyl) ruthenium (from Colonial Metals Inc., Elkton, MD, USA) are dissolved in 50 ml of diethyl ether. At room temperature, 0.51 ml (3.77 mmol) of a 54% strength HBF4-Et20 solution (from Aldrich) is added dropwise over a period of 10 minutes. After the addition is complete, the mixture is allowed to settle and the completeness of the precipitation is checked by addition of a further drop of HBF4-Et20. The supernatant solvent is taken off and the solid is washed twice with diethyl ether. The light-yellow residue is dried under reduced pressure. Yield: 1.43 g (100%). b) Preparation of the_____acetonitrile complex (115-2, 4-dimethylpentadienyl) - (CH3CN) 3rutheni\am(II) te tra fluoroborate 0.41 g of (1.1 mmol) of (Ti4-2,4-dimethylpentadiene-Ti2- C,H) -115-2, 4-dimethylpentadienyl)rutheniiam tetrafluoro- borate; prepared in step a) , is admixed with 10 ml of acetonitrile. The orange solution is stirred for 10 minutes and the solvent is then removed under reduced pressure to give an orange solid. Yield: 0.44 g (100%). c) Reaction with Taniaphos T 001-1 Taniaphos SL-TOOl-1 (from Solvias, Basel, CH; 400 mg, 0.58 mmol) is placed in a round-bottom flask provided with a magnetic stirrer and the Ru starting compound (236 mg, 0.58 mmol) prepared in b) is then added. The reactants are dissolved in 10 ml of CH2CI2 and the mixture is stirred at room temperature for three hours. The solution becomes deep red. The solvent is taken off under reduced pressure and the solid residue is washed with diethyl ether. The product is collected and dried in a high vacuum. Yield: 90%, red-orange solid, two diastereomers having a de of 75%. Characterization: 1H NMR (CD2Cl2, major) 5: -1.76 (b, IH, pentadienyl) , 0.15 (b, IH, pentadienyl). 0.765 (t, IH, J = 6.41 Hz, pentadienyl) , 1.24 (b, 3H. pentadienyl-CH^) , 1.81 (s, 6H, N(CH3)2), 2.34 (m, 3H. pentadienyl-CHj) , 2.88 (s, 3H, CH3CN) , 3.63 (b, IH) , 3.66 (m, IH) , 3.76 (s, 5H) , 4.39 (t, IH, J = 2.4 Hz), 4.87 (m, IH) , 4.89 {m, IH) , 5.90 (s, IH) , 6.02 (t, 2H) , 6.90-8.20 {m, 21H) , 8.80 (dd, IH, J = 7.6 Hz, J = 14.3 Hz). "P NMR (CD2CI2) S: 36.54 (d, Jpp = 34.6 Hz), 31.59 (d, Jpp = 34.6 Hz), "f NMR (CD2CI2) 5: -149.87 (s) . The P-P coordination according to the invention is evidenced by the fact that 2 P signals having chemical shifts which are relatively close together (8: 36.54 ppm (d, J^p = 34.6 Hz) and 31.59 ppm (d, Jpp = 34.6 Hz)) occur in the 31P NMR and a coupling between P(l) and P(2) of 34.6 Hz is observed. Signals of a noncoordinated P atom are not found. The complex according to the invention gives vejry good yields when used as catalyst for enantioselective catalytic hydrogenation. Example 2 Preparation of (ti5-2,4-dliiisthylpentadienyl) (iodo)- (Taniaphos TOOl-1)ruthenium(II) The Taniaphos complex (115-2,4-dimethylpentadienyl)- (CH3CN) (Taniaphos TOOl-1)ruthenium (II) tetrafluoro- borate is prepared as described in exeuttple Ic) . 100 mg of this compoiind are dissolved in 4 ml of acetone, an excess of 2 equivalents of potassium iodide (80 mg) is added and the mixture is stirred at room temperature for 10 hours. The precipitated solid is filtered off and washed firstly with water and then with cold acetone. This gives a mixture of two diastereomers having a de of 60% as a yellow-orange solid in a yield of 85%. Characterization: 1H NMR (CD2CI2, major) 6: -2.06 (m, IH) , -0.13 (m, IH) , 0.93 (m, IH) , 1.29 (s, 3H), 1.95 (s, 6H>, 2.81 (s, 3H), 3.28 (m, IH), 3.76 (m, IH), 3.80 (s, 5H), 4.17 (m, IH), 4.75 (m, IH) , 5.54 (m, IH) , 6.07 (m, 2H) , 6.6-7.8 (m, 21H), 9.25 (m, IH) , 9.63 (m, IH) . ^^P NMR (CD2CI2) 5: 39.88 ppm (d, Jpp = 40.5 Hz), 29.96 mm (d, Jpp = 40.5 Hz). MS (FAB) m/e: 1012 [M*+l] , 884 [M*-I], 788 [M*-I-pentadienyl] . The P-P coordination according to the invention is evidenced by the fact that only 2 P signals having chemical shifts which are relatively close together (6: 39.88 ppm and 29.96 ppm) occur in the ¦'^P NMR and a coupling of 40.5 Hz between P(l) and P(2) is observed. Use for catalytic hydrogenation: The (Taniaphos TOOl-1)(iodo)ruthenium(II) complex prepared as described in example 2 is used for the asyimnetric hydrogenation of trans-2-methyl-2-butenoic acid. The hydrogenation is carried out in an autoclave under 50 bar of hydrogen; solvent: methanol; ten^erature: 50°C. A little methanolic HCl is added. After a reaction time of 18 hours, the hydrogen pressure is vented. Analysis of the crude material indicates a conversion of > 90% and an enantiomeric excess (ee) of > 40%. The substrate/catalyst ratio (S/C) is > 500. The complex according to the invention thus gives very good results when used as catalyst for enantioselective catalytic hydrogenation. Exanple 3 Preparation of (T]5-2,4-diinethylpentadieny-l) (lodo)- (Tanlaphos "OH) rutheniua (II) In a round-bottom flask provided with a magnetic stirrer, the acetonitrile complex (ti5-2, 4-diraethyl- pentadienyl) (CH3CN)3ruthenivun{II) tetraf luoroborate prepared as described in example lb) (288 mg, 0.71 iranol] is dissolved in 15 ml of methylene chloride and stirred with (S, S)-Taniaphos-OH (288 mg, 0.71 mmol) at room tenperature for 3 hours. The solution becomes deep red. The solvent is removed under reduced pressure and the residue is washed with diethyl ether. The (Taniaphos-OH)ruthenium(II) tetrafluoroborate complex obtained is not isolated further but dissolved in 20 ml of acetone. Excess potassium iodide (33 0 mg, 2 mmol) is added and the solution is stirred for a further 10 hours. The precipitated yellow-orange solid is filtered off and washed with water and acetone. This gives a product comprising a mixture of two diastereomers in a virtually equimolar ratio. Yield: 90%. The P-P coordination of the Taniaphos-OH ligand is evidenced by the ^^P-NMR. The Ru complex gives good yields when used as catalyst for enantioselective catalytic hydrogenation. CoMparative Preparation of an Ru coanplex with P-monocoordinated £erroce]^ldiplioaphine ligaads The reaction of Taniaphos SL-TOOl-1 with the commercially available ruthenivim complex [RuCl2(p- cumene)]2 (from Umicore, Hanau) in THF at room teit^perature gives, in accordance with equ. (1), a 2:1 mixture of two Isomers which were identified as P-monocoordinated complexes by means of '^P spectroscopy. The spectrum displays four different signals (•'^P NMR in CD2CI2: 5 = 49 ppm and -13 ppm for the isomer present in the lesser amount, 5 = 35 ppm and -15 ppm for the predominant isomer) . Here, the signals having a negative chemical shift (5 = -13 ppm and -15 ppm) can be assigned to the noncoordinated P atoms of the ligand in each case. When the mixture is refluxed for 2 hours, the isomer which is present in the predominant proportion is formed; isolation is effected by precipitation with hexane. Bidentate P-P coordination of the ferrocenyl- diphosphine ligand is not observed. Use for catalytic hydrogenation: The Ru complex mixture prepared as described in con^jarative example 1 is used for the asymmetric hydrogenation of treins-2-methyl-2-butenoic acid. The hydrogenation is carried out in an autoclave lander 50 bar of hydrogen; solvent: methanol; tenperature: 50°C. A little methanolic HCl is added. After a reaction time of 18 hours, the hydrogen pressure is vented. Analysis of the crude material indicates incomplete reaction and an ee of substrate/catalyst ratio (S/C) is 200. These results can be compared with the results of exeuiple 2. They demonstrate the superiority of the Ru complexes of the invention having P-P coordination of the ferrocenyldiphosphine ligands in the asyiranetric hydrogenation of chiral organic confounds. Claims 1. A ruthenium conplex with a chiral ferrocenyl- diphosphine ligand for homogeneous catalysis corresponding to the general formula where Ru is in the oxidation state +11, n is an integer equal to or greater than 3, Ld is an neutral ligand, Z is at least one n-bonded organic ligand, E' is the anion of an oxo acid or conplex acid and Lz is at least one anionic ligand and the ferrocenyldiphosphine ligand P{l)-P(2) has bidentate P-P coordination. 2. The ruthenium conplex as claimed in claim 1, wherein the chiral ferrocenyldiphosphine ligand P(l)-P(2) together with the ruthenium forms an at least eight-membered ring. 3. The ruthenivun complex as claimed in claim 1 or 2, wherein the chiral ferrocenyldiphosphine ligand P(l)-P(2) is selected from the group consisting of Taniaphos, Taniaphos-OH, Taniaphos-OMe and Walphos ligands. 4. The ruthenium complex as claimed in any of claims 1 to 3, wherein Ld is selected from the class of 2-electron donor ligemds and encompasses secondary or tertiary phosphines or N-heterocyclic carbene ligands (known as NHC ligands). 5. The ruthenium complex as claimed in any of claims 1 to 4, wherein Ld is a solvent ligand selected from the group consisting of acetonitrile (CH3CN), diethyl ether (DEE), water (H2O) , acetone, tetrahydrofuran (THF), dioxane, pyridine, imidazole and thiophene. 6. The ruthenium conplex as claimed in any of claims 1 to 5, wherein Z is at least one substituted or unsubstituted cyclic or open-chain dienyl ligand, for example at least one substituted or \insubstituted pentadienyl or hepta- di eny1 1igand. 7. The ruthenium complex as claimed in any of claims 1 to 6, wherein Z is at least one ligand selected from the group consisting of 2,4-di- methylpentadiene, 2,3,4-trimethylpentadiene, cycloheptadiene, cyclooctadiene and norbornadiene. 8. The ruthenivun conrplex as claimed in any of claims 1 to 7, wherein E" is an anion selected from the group consisting of HSO4', CF2SO3', CIO4", BF4', B(aryl)4", SbFg" and PFs". 9. The ruthenium complex as claimed in any of claims 1 to 8, wherein Lj is at least one anionic ligand selected from the group consisting of halides and pseudohalides. 10. The ruthenium coit^lex as claimed in any of claims 1 to 9, wherein (S)-l-diphenylphosphino-2- [ (R) -a- (N,N-dimethylamino) -o- (diphenylphosphino- phenyl)methyl]ferrocene (= Taniaphos TOOl-1); (R) -l-diphenylphosphino-2- [ (S) -a- (N, N-dimethyl- amino) -o- (diphenylphosphinopheny 1) methyl] ferrocene (= Taniaphos TOOl-2); (S)-1-dicyclohexylphosphino- 2- [ (R) -a- (N,N-dijnethylamino) (dicyclohexyl- phosphinophenyl)methyl]ferrocene {= Taniaphos T002-1) or (R)-l-dicyclohexylphosphino-2-[(S)-a- (N,N-dimethylamino) (dicyclohexylphosphinophenyl) - methyl]ferrocene (= Taniaphos T002-2) is used as chiral ferrocenyldiphosphine ligand. 11. A process for preparing ruthenium complexes with a chiral ferrocenyldiphosphine ligand which has bidentate P-P coordination, characterized in that an Ru starting conpound of the general fonmila IZ-RU-(I.D)a]*B- where Ru is in the oxidation state +11, n is an integer equal to or greater than 3, Ld is an neutral ligand, Z is at least one n-bonded organic ligand and E is the anion of an oxo acid or complex acid, is reacted with a chiral ferrocenyldiphosphine ligand. 12. The process as claimed in claim 11, wherein the chiral ferrocenyldiphosphine ligand is selected from the group consisting of Taniaphos, Taniaphos-OH, Taniaphos-OMe and Walphos ligands. 13. The process as claimed in claim 11 or 12, wherein Ld is selected from the class of 2-electron donor ligands and encompasses secondary or tertiary phosphines or N-heterocyclic carbene ligands (known as NHC ligands). 14. The process as claimed in any of claims 11 to 13, wherein Lp is a solvent ligand selected from the group consisting of acetonitrile (CH3CN) , diethyl ether (DEE), water (HjO), acetone, tetrahydrofuran (THF), dioxane, pyridine, imidazole and thiophene. 15. The process as claimed in any of claims 11 to 14, wherein Z is at least one substituted or unsubstituted cyclic or open-chain dienyl ligand, for excunple at least one substituted or unsubstituted pentadienyl or heptadienyl ligand. 16. The process as claimed in any of claims 11 to 15, wlierein Z is at least one ligand selected from the group consisting of 2,4-dimethylpentadiene, 2,3,4-trimethylpentadiene, cycloheptadiene, cyclo- octadiene and norbomadiene. 17. The process as claimed in any of claims 11 to 16, wherein E" is an anion selected from the group consisting of HSO4', CF3SO3', C104', BF4', B(aryl)4', SbF6~ and PF6". 18. The process as claimed in any of claims 11 to 17 which further comprises replacement of at least one neutral ligand Ld by at least one anionic ligand Lz selected from the group consisting of halides and pseudohalides. 19. A ruthenium complex with a chiral ferrocenyl- diphosphine ligand, which has bidentate P-P coordination to the Ru(II) and can be obtained by a process as claimed in any of claims 11 to 18. 20. The use of the ruthenium complexes as claimed in any of claims 1 to 10 as catalysts for homogeneous asytnmetric catalysis for preparing organic compounds. 21. The use of the ruthenivun complexes as claimed in any of claims 1 to 10 as catalysts for the homogeneous asymmetric catalytic hydrogenation of organic compounds. 22. The use of the ruthenium complexes as claimed in any of claims 1 to 10 as catalysts for the enantioselective hydrogenation of C=C, C=0 or C=N multiple bonds. The invention relates to ruthenium complexes with a chiral ferrocenyldiphosphine ligand, wherein the ruthenium has the oxidation state (+II) and the chiral ferrocenyldiphosphine ligand has bidentate P-P coordination to the ruthenium. The ruthenium complexes are cyclic and with the ferrocenyldiphosphine ligand have an at least eight-membered ring. The ferrocenyldiphosphine ligands are selected from the group consisting of Taniaphos, Taniaphos-OH and Walphos ligands. A process for preparing the Ru complexes is described. The Ru complexes are used as catalysts for homogeneous asymmetric catalysis for preparing organic compounds.

Documents:

3866-KOLNP-2009-(03-09-2014)-PETITION UNDER RULE 137.pdf

3866-kolnp-2009-abstract.pdf

3866-kolnp-2009-claims.pdf

3866-KOLNP-2009-CORRESPONDENCE 1.1.pdf

3866-KOLNP-2009-CORRESPONDENCE 1.2.pdf

3866-kolnp-2009-correspondence.pdf

3866-kolnp-2009-description (complete).pdf

3866-kolnp-2009-form 1.pdf

3866-KOLNP-2009-FORM 18.pdf

3866-kolnp-2009-form 2.pdf

3866-kolnp-2009-form 3.pdf

3866-kolnp-2009-form 5.pdf

3866-kolnp-2009-international publication.pdf

3866-kolnp-2009-international search report.pdf

3866-KOLNP-2009-PA.pdf

3866-kolnp-2009-pct priority document notification.pdf

3866-kolnp-2009-pct request form.pdf

3866-kolnp-2009-specification.pdf

3866-KOLNP-2009-TRANSLATED COPY OF PRIORITY DOCUMENT.pdf