Title of Invention

PROCESS FOR THE PREPARATION OF IRIDIUM ACETATE

Abstract The present invention relates to a process or the preparation of indium acetate comprising the steps (a) reacting an indium compound with an alkaline compound in a protic solvent to obtain an iridium containing precipitate, where the reaction is conducted in the presence of at least one component (i) selected from oxalic acid, a slat of oxalic acid, a salt of oxalic acid, formic acid and a salt of formic acid, (b) reacting the precipitate in the presence of at least (i) one compound selected from oxalic acid, a salt of oxatic acid, formic acid and a salt of formic acid, and (ii) CH3CH2H and/or CH3(CO)O(CO)CH3 to give an iridium acetate containing solution. The invention also relates to indium acetate having a low halide content, to an indium containing precipitate and to uses of the iridium containing precipitate of the present invention and the iridium acetate of the present invention.
Full Text WO 2006/125628 PCT/EP2006/004964
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PROCESS FOR THE PREPARATION OF IRIDIUM ACETATE
The present invention relates to a process for the preparation of iridium acetate and to the
iridium acetate obtainable according to that process. Additionally, the present invention
relates to a process for the preparation of an iridium containing precipitate and applications
of the precipitate and the iridium acetate (as a solid or in solution).
The present invention also relates to iridium acetate having a low halide content, as a solid or
as a solution, an iridium containing precipitate having a low halide content and a process for
the preparation of these products.
The invention also relates to the use of the iridium acetate having a low halide content of the
present invention and of the corresponding iridium acetate solution as a catalyst or a catalyst
precursor in homogeneously or heterogeneously catalyzed reactions, selected from the group
consisting of carbonylation reactions, hydroformylation reactions, coupling reactions,
oxidation reactions, hydrogenation reactions, and hydrosilylation reactions, in electroplating,
or for the preparation of catalysts for heterogeneous catalysis.
A widespread application of iridium and compounds or complexes of iridium is their use as a
catalyst for various chemical reactions, such as isomerization reactions, hydroformylation
reactions or carbonylation reactions. Recently, particularly carbonylation reactions catalyzed
by iridium or its compounds have gained in importance. One example is the iridium
catalyzed carbonylation of methanol (with carbon monoxide) resulting in acetic acid or a
reactive derivative thereof, referred to as Cativa process. Green iridium acetate was, inter
alia, described as a suitable iridium compound for that process (EP-A-0 849 248).
Processes for the preparation of iridium carboxylates were already described in the past. For
example, a process is known from WO-A-96/23757, in which at least one chloride or
bromide compound of iridium is reacted with an alkali or alkaline earth carboxylate in a
medium containing a carboxylic acid to give an iridium carboxylate containing solution. To
be able to use the solution for catalytic purposes, the alkali and alkaline earth chlorides and
bromides obtained with this process as byproducts of the reaction are separated using ion

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exchange columns, wherein the alkali metal or alkaline earth metal ions are separated using a
cationic ion exchange resin and the chloride or bromide ions are separated using an anionic
ion exchange resin.
The process yields indium acetate solutions with chloride contents below 0.0020% by
weight, wherein these values are based on the iridium containing solution. The described
solutions, however, have iridium contents of 1.65% by weight Ir (example 2) and 0.62% by
weight Ir (example 3), resulting in a content of 1212 and 3225 ppm chloride, respectively,
based on the proportion of iridium. These chloride contents are still too high for certain
applications in catalysis.
The process according to WO-A-96/23757 has the further disadvantage that the ion exchange
materials required for the separation of chloride and bromide ions interfering with catalytic
purposes are expensive. Furthermore, the process takes much time due to the time needed for
the double ion exchange and the necessary regeneration of the column materials.
Furthermore the ion exchange may lead to losses in yield.
From EP-A-1 046 629 a process for the preparation of iridium acetate is known, wherein
iridium hydroxide is precipitated from an aqueous solution of an iridium chloro compound
using an aqueous solution of an alkali metal hydroxide, carbonate or hydrogen carbonate, the
precipitated iridium hydroxide is separated and reacted with acetic acid or a mixture of acetic
anhydride to give an iridium acetate containing solution and the iridium acetate is isolated
from the solution as a solid. To obtain iridium acetate with a low chloride content, the
iridium hydroxide is preferably reprecipitated prior to the reaction with acetic acid. To this,
the iridium hydroxide is dissolved with nitric acid or with a mixture of nitric acid and
hydrogen peroxide and iridium hydroxide is reprecipitated from the formed solution by
addition of an aqueous solution of an alkali metal hydroxide, carbonate or hydrogen
carbonate. The iridium acetate isolated from the dark green solution is described as a dark
green, glossy solid. The process, however, requires the isolation of the iridium acetate first
obtained in aqueous solution as a solid, which is typically performed by evaporation
optionally under vacuum. This isolation step is not only disadvantageous, because the
evaporation of the aqueous solution takes a very long time (and therefore adversely affects
the price of the product), but also bears the danger of decomposition or change of the
product. Furthermore the reported yields leave room for improvement.
Furthermore, in the course of the studies leading to the present invention it turned out, that
the iridium acetate, described in EP-A-1 046 629 as "being low in chloride content" without
giving any exact values, still contains amounts of chloride impurities even after performing

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the reprecipitation recommended in that description to reduce the chloride content. The
obtained amounts of chloride impurities are too high and thus need improvement particularly
with regard to the desired application for catalytic purposes
Based on these findings it was an object of the present invention to provide an inexpensive
process for the preparation of iridium acetate, whereby iridium acetate can be obtained in
high yield and in high purity.
Another object of the present invention was to provide iridium acetate having a low halide
content and to provide an inexpensive process for the preparation thereof. Iridium acetate
should be obtained in high yield and in high purity, particularly with a low halide content.
These objects have been achieved by the surprising finding that iridium acetate can be
obtained in high yield and in high purity, when the process as defined in the claims, is
conducted in the presence of at least one compound, selected from oxalic acid, a salt of
oxalic acid, formic acid and a salt of formic acid (subsequently oxalic acid, a salt of oxalic
acid, formic acid and a salt of formic acid are briefly referred to as "component (i)").
The present invention thus relates to a process for the preparation of iridium acetate
comprising the steps of:
(a) reacting an iridium compound with an alkaline compound in a protic solvent to obtain
an iridium containing precipitate, wherein the reaction is conducted in the presence of
at least one compound selected from oxalic acid, a salt of oxalic acid, formic acid and a
salt of formic acid, and
(b) reacting the precipitate, optionally after separation, in the presence of
(i) at least one compound selected from oxalic acid, a salt of oxalic acid, formic acid
and a salt of formic acid, and
(ii) CH3CO2H and/or CH3(CO)O(CO)CH3 (subsequently briefly referred to as
component (ii))
to give an iridium acetate containing solution, and
(c) optionally isolating the iridium acetate as a solid from the solution.
The present invention also relates to a process for the preparation of an iridium containing
precipitate, the process comprising step (a) as defined above, and to the iridium containing
precipitate obtainable according to that process.
Furthermore, the present invention relates to an iridium acetate having a halide content of

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less than 1000 ppm, preferably less than 800 ppm (based on Ir), which is obtainable, for
example, by the process of the present invention. Additionally, the present invention relates
to an iridium containing precipitate having a halide content of less than 1000 ppm and
preferably less than 800 ppm (based on Ir), and which is obtainable, for example, as an
intermediate in the process of the present invention.
Furthermore the present invention relates to the use of the iridium acetate of the present
invention or of the iridium containing precipitate as a catalyst or a catalyst precursor in
homogeneously or heterogeneously catalyzed reactions, selected from carbonylation
reactions, hydroformylation reactions, coupling reactions, oxidation reactions, hydrogenation
reactions, hydrosilylation reactions and isomerization reactions, and to the use in
electroplating.
In the present invention the term "at least one compound selected from (the listed
possibilities)" means that one compound from the listed possibilities is required to be present
and more than one compound from the listed possibilities, i.e. for example a mixture of two
or three or more of the listed possibilities, may be present.
The term "ammonium" in the present invention means a quaternary ammonium ion
represented by the formula [NR1R2R3R4]+, wherein R1, R2, R3, and R4 are independently
selected from a hydrogen atom and a lower alkyl group (preferably a C1 to C6, alkyl group),
that may be linear, branched or cyclic. Preferably at least one of R1 to R4 represents a
hydrogen atom and particularly preferably all of R1 to R4 represent a hydrogen atom.
In the present invention the term "iridium acetate" means a compound having iridium
atom(s) and acetate and is to be understood in this broad sense.
The term "protic solvent" in the present invention means a solvent containing or able to
release protons and/or able to form hydrogen bonds. Examples of protic solvents useful in
the present invention are water and alcohols, e. g. C1-C6 alkanols (preferably methanol,
ethanol, n-propanol, iso-propanol, n-butanol, sec-butanol, tert-butanol), and mixtures of two
or more of these solvents. Preferred protic solvents for the purposes of the present invention
are water and a mixture of water and a C1-C6 alkanol (preferably methanol). However, the
present invention is not limited to these specific solvents. Suitable mixing ratios can readily
be determined by one of ordinary skill in the art.
In the present invention the term "inert gas" means a gaseous atmosphere, which is inert
towards the starting compounds, the reaction mixture or the reaction products, respectively,

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i. e. will neither chemically nor physically alter them. Specifically the inert gas used is
preferably essentially free of oxygen. Inert gases suitable for the purposes of the present
invention include, but are not limited to for example nitrogen, argon or other noble gases and
mixtures thereof. Herein, the term "essentially free of oxygen" means, that the amount of
oxygen that might be present in the inert gas atmosphere is in a range that does not adversely
affect the course of the reaction, the yield and purity of the intermediates and end products.
The amount of oxygen in the inert gas atmosphere that is still acceptable for the purposes of
the present invention is about 2 percent by volume. Typically, the amount of oxygen in the
inert gas atmosphere is less than about 1000 ppm, more preferably less than about 500 ppm
(in terms of ideal volume fractions, i.e. parts by moles).
This can be achieved, for example, by using industrial inert gases having a purity of about
99.99% by volume. The amount of oxygen contained in the inert gas used may for example
be, but is not limited to, less than about 100 ppm.
In the following the process of the present invention will be described: The steps (a) and (b)
will be described in detail.
Step (a)
Step (a) comprises reacting an iridium compound with an alkaline compound in a protic
solvent to obtain an iridium containing precipitate. According to the present invention the
reaction is conducted in the presence of at least one compound, selected from oxalic acid, a
salt of oxalic acid, formic acid and a salt of formic acid (component (i)).
The salts of oxalic acid and the salts of formic acid are not particularly limited. Basically,
any salt of oxalic acid or formic acid may be used. Usually, the salt will be selected so that it
is soluble in the protic solvent under the chosen reaction conditions.
Suitable oxalic acid salts include, but are not limited to, ammonium salts, alkali salts (i. e.
lithium, sodium, potassium and cesium salts) and alkaline earth salts (i. e. magnesium,
calcium, barium and strontium salts) of oxalic acid. Preferred examples include the sodium
salt, the magnesium salt and ammonium salts of oxalic acid.
Suitable formic acid salts include, but are not limited to, ammonium salts, alkali salts (i. e.
lithium, sodium, potassium and cesium salts) and alkaline earth salts (i. e. magnesium,
calcium, barium and strontium salts) of formic acid. Preferred examples include the sodium

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salt, the calcium salt and ammonium salts of formic acid.
For performing of step (a) either one single compound, selected from component (i), or a
mixture of several compounds, selected from component (i), may be used.
In a preferred embodiment, step (a) is conducted in the presence of oxalic acid and/or
ammonium oxalate.
The iridium compound used as a starting material is not particularly limited. Thus the term
"iridium compound", as used herein, is to be interpreted in a broad sense and includes both
stoichiometric and non-stoichiometric compounds of iridium. The iridium compounds may
also be complex-like compounds of iridium.
In the practice of the invention it has proven useful to use an iridium compound as a starling
material, that can be dissolved in the protic solvent used for the reaction.
The oxidation state of the iridium in the iridium compound is not limited. Preferably the
iridium is present in the oxidation state (0), (+1), (+III) or (+IV), preferably (+III) or (+IV),
particularly preferably in the oxidation state (+IV). It is also possible for the iridium
compound used as a starting material to contain iridium in a first oxidation state as well as
iridium in a second (different from the first) oxidation state, for example iridium in the
oxidation state (+III) as well as in the oxidation state (+IV). As examples of such iridium
compounds mixed iridium(III)/iridium(lV) halides and their hydrates can be mentioned.
From an economical viewpoint the use of readily available, e. g. commercially available, and
inexpensive iridium compounds is preferred.
In a preferred embodiment the iridium compound is selected from iridium halogen (i. e.
chlorine, bromine, or iodine, preferably chlorine) compounds, including but not limited to
iridium(III) chloride, iridium(III) bromide, iridium(III) iodide, iridium(lll) chloride hydrate,
iridium(III) bromide hydrate, iridium(III) iodide hydrate, iridium(IV) chloride, iridium(IV)
bromide, iridium(IV) iodide, iridium(lV) chloride hydrate, iridium(IV) bromide hydrate,
iridium(IV) iodide hydrate, iridium(III)/iridium(IV) chloride, iridium(III)/iridium(IV)
bromide, iridium(IiI)/iridium(lV) iodide, iridium(III)/iridium(IV) chloride hydrate,
iridium(IlI)/iridium(IV) bromide hydrate, iridium(HI)/iridium(IV) iodide hydrate,
hexachloroiridium(III) acid and its ammonium, alkali (preferably sodium and potassium) and
alkaline earth (preferably magnesium and calcium) salts, hexabromoiridium(ITI) acid and its
ammonium, alkali (preferably sodium and potassium) and alkaline earth (preferably

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magnesium and calcium) salts, hexachloroiridium(IV) acid and its ammonium, alkali
(preferably sodium and potassium) and alkaline earth (preferably magnesium and calcium)
salts, hexabromoiridium(IV) acid and its ammonium, alkali (preferably sodium and
potassium) and alkaline earth (preferably magnesium and calcium) salts. Also suitable are
amine chloro complexes of the formula [IrCln(NH3)6-n](3 n)+ optionally having one or more
counter ions for charge equalization (e. g. alkali, alkaline earth, or chloride ions), wherein n
is an integer of 1 to 5, or compounds, such as [Ir(CO)2Cl]2, Ir4(CO)]2 or Ir(acac)3.
With respect to the solubility in the protic solvent used and from an economical viewpoint
the use of hexachloroiridium(III) acid and its sodium, potassium and ammonium salts,
hexachloroiridium(IV) acid and its sodium, potassium and ammonium salts and of mixed
iridium(IIl)/iridium(lV) halides and hydrates thereof is preferred. The use of Na2lrCl(,,
K2IrCl6, (NH4)2IrCl6, H2IrCl6, Na3IrCl6, K3IrCl6, (NH4)3IrCl6-,, H3IrCl6 and
iridium(+III)/iridium(+IV) chloride (hydrate) is particularly preferred.
A mixture of two or more different iridium compounds may also be used.
Examples of protic solvents useful in step (a) of the present invention are water and alcohols,
e. g. C1-C6 alkanols (preferably methanol, ethanol, n-propanol, iso-propanol, n-butanol, scc-
butanol, tert-butanol), and mixtures of two or more of these solvents. Preferably water or a
mixture of water and a C1-C6 alkanol (preferably methanol) is used as a protic solvent.
The alkaline compound is selected from substances, the solutions of which exhibit an
alkaline reaction in the presence of the protic solvent used. Examples of alkaline compounds
suitable in the present invention are hydroxides of ammonium, alkali metals (i. e. Li, Na, K,
Rb, Cs) or alkaline earth metals (i. e. Mg, Ca, Ba, Sr), carbonates and hydrogen carbonates of
ammonium, alkali metals (i. e. Li, Na, K, Cs) or alkaline earth metals (i. e. Mg, Ca, Ba, Sr) or
amines of the formula NR1R2R3, wherein R1, R2 and R3 are independently selected from a
hydrogen atom and C1-C6 alkyl groups (such as ammonia, triethyl amine and trimethyl
amine). As the alkaline compound preferably an alkali metal hydroxide is used, more
preferably sodium hydroxide or potassium hydroxide and most preferably potassium
hydroxide is used. A mixture of two or more alkaline compounds may also be used.
The alkaline compound may be used as such or dissolved in one or more protic solvent(s), as
defined above. Preferably the alkaline compound is at least partially dissolved in the protic
solvent (mixture).
To generate a precipitate it has proven advantageous to use the alkaline compound as

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solution in a protic solvent (preferably water) in a concentration of at least 1% by weight,
preferably at least 5% by weight, more preferably in a concentration of 10 to 30% by weight,
based on the protic solvent used.
The alkaline compound is preferably used in an amount, based on iridium, significantly
higher than the stoichiometric amount. The ratio of the alkaline compound (in moles, based
on a monohydric alkaline compound) to iridium (moles) may for example be more than 2,
preferably 3 to 20, particularly preferably 7 to 14. A suitable amount of the iridium
compound is e. g. 0.5 to 15% by weight, preferably 1 to 8% by weight, particularly
preferably 1.5 to 5% by weight, based on the starting solution used.
The compound selected from component (i) is preferably used in at least an about equimolar
amount (e. g. at least 0.8 mol equivalents, more preferably at least 1.0 mol equivalent, even
more preferably 1.05 to 1.5 mol equivalents, based on iridium). When a mixture of
compounds of the component (i) is used, the amounts shown refer to the total number of
moles of the selected compounds.
Step (a) is preferably conducted in an atmosphere of inert gas. Hence in a preferred
embodiment both the reaction apparatus and the reactants used are rendered oxygen free by
purging with an inert gas in a per se known manner.
To obtain an iridium containing precipitate having good filtration properties step (a) is
preferably conducted at a pH of about 6 to about 10, preferably of about 7 to about 9,
particularly preferably at a pH of about 7.5.
It has also proven advantageous to conduct step (a) with heating for example at 50 to 120 °C,
particularly 60 to 110 °C, more preferably 70 to 95 °C. If step (a) is conducted with heating,
it is preferable to cool or allow to cool the reaction mixture to room temperature prior to
performing step (b).
The addition of the iridium compound, of the alkaline compound, of said at least one
compound selected from component (i) and of the protic solvent may be performed in any
order. For example, first the protic solvent may be added and the iridium compound, the
alkaline compound and the compound selected from component (i) may be added in any
order or simultaneously.
Although the addition of the iridium compound and of the alkaline compound may be
performed in any order, it may be advantageous to first form a mixture (preferably solution)

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comprising the indium compound and at least one compound selected from component (i) in
the protic solvent.
Accordingly, in a preferred embodiment of the invention step (a) comprises the substeps (al)
and (a2). In the present invention every reference to step (a) is to be understood as well as a
reference to the preferred embodiment comprising the substeps (al) and (a2), unless stated
otherwise.
Substep(al)
Substep (al) comprises forming a mixture (preferably solution) comprising the iridium
compound and at least one compound selected from component (i), and the protic solvent
optionally with heating.
The addition in substep (al) may be performed in any order. For example first a mixture
(preferably solution) comprising the iridium compound and a protic solvent, each defined as
above, may be formed, to which at least one compound selected from component (i),
optionally dissolved in a protic solvent, is added. The opposite order is acceptable as well.
The addition may be performed independently from the order under the conditions
subsequently defined for step (a).
Substep (al) is preferably performed with heating for example at 50 to 120 °C, particularly
60 to 110 °C, more preferably 70 to 95 °C. Particularly preferably, the elevated temperature
in step (al) is maintained for a prolonged period of time, for example for a period of several
minutes, particularly more than 10 minutes, preferably more than 30 minutes, even more
preferably about 45 minutes to 3 hours.
Substep (al) is preferably conducted in an atmosphere of inert gas.
Substep (a2)
Substep (a2) comprises reacting the mixture (preferably solution) obtained in step (al) with
the alkaline compound (as defined above) to obtain an iridium containing precipitate,
optionally with heating.
The addition in substep (a2) may be performed in any order. For example, first the mixture
(preferably solution) obtained in substep (al) may be added and the alkaline compound,
optionally dissolved in a protic solvent, can be added thereto, or, conversely, first a mixture

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(preferably solution) comprising the alkaline compound and a protic solvent, each as defined
above, may be formed, to which the mixture obtained in substep (al) is added.
In a preferred embodiment substep (a2) is performed such that first the mixture (preferably
solution) obtained in substep (al) is prepared and a solution comprising the alkaline
compound and the protic solvent is added.
Substep (a2) is preferably performed with heating for example at about 50 to about 120 °C,
preferably about 60 to about 110 °C, more preferably about 80 to about 95 °C. Particularly
preferably the elevated temperature in substep (a2) is maintained for a prolonged period of
time, for example for a period of several hours, particularly more than 10 hours, preferably
more than 15 hours, even more preferably more than 30 hours. The reaction time has no
upper limit, but is typically less than 100 hours, preferably less than 90 hours, particularly
preferably less than 80 hours. Most preferably, the reaction time is approximately 40 hours.
Substep (a2) is preferably conducted in an atmosphere of inert gas.
Independently from the order of the addition of the iridium compound, the alkaline
compound and the compound selected from component (i), the addition in step (a) and
substeps (al) and (a2) is typically performed with stirring. Independently from the order of
the addition the addition may be performed for example by adding one single portion (i. e. as
fast as possible) or by adding the substances to be added dropwise or in small amounts
respectively over a period of a few seconds to several hours, e. g. within 10 seconds to 3
hours, preferably within 1 minute to 60 minutes.
In one embodiment of the invention the pH of the reaction mixture is adjusted to a value of
about 6 to about 9, preferably to about 7 to about 8.5, after completion of step (a) (i. c. after
obtaining an iridium containing precipitate) and prior to performing step (b). The pH may be
adjusted by adding either an additional amount of the alkaline compound, as defined above,
or by adding a weakly acidic compound, such as diluted acetic acid or hydrochloric acid and
mixtures thereof.
To keep the halide content small for a later use as a catalyst, the pH is preferably not adjusted
with an acid, that may additionally introduce halide ions into the reaction mixture.
In the practice of the invention, acetic acid in a concentration of about 0.5 to 100% by
weight, preferably 35 to 65% by weight, particularly preferably about 50% by weight (in
water) has proven useful as a means to adjust the pH.

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Step (a) may comprise one or more optional substeps selected from separating, washing and
reprecipitating the obtained iridium containing precipitate.
Particularly when a halide containing iridium compound is used, carrying-out of separating
and washing the iridium containing precipitate may advantageously affect the halide content
of both the iridium containing precipitate and the iridium acetate obtainable therefrom.
Particularly for a later application as a catalyst or catalyst component for homogeneously or
heterogeneously catalyzed reactions the halide content should be as low as possible.
Suitable conditions for the optional separation and the optional washing of the precipitate
may be determined by one of ordinary skill in the art by routine tests. The following
conditions are therefore not to be construed as limiting the invention.
The optional separation of the obtained precipitate may be conducted by operations such as
filtration, suction filtration, sedimentation or centrifugation. When separating the precipitate
it may prove advantageous to avoid complete drying of the precipitate.
The optional washing step of the precipitate may be conducted for example with a suitable
washing liquid. As a washing liquid any liquid may be used, that is inert towards the
precipitate of iridium hydroxide, i. e. that neither reacts with nor dissolves the same. Suitable
washing liquids are for example water, acetic acid, hydrochloric acid and mixtures thereof.
To avoid the introduction of halide ions into the precipitate, however, halide free washing
liquids, such as water and acetic acid and mixtures thereof (e. g. 5 to 20% by weight acetic-
acid, particularly preferably 8 to 12% by weight acetic acid) are preferably used as washing
liquids. In cases though, where the halide content is not critical, a halide containing washing
liquid, such as hydrochloric acid diluted with water, may also be used. The washing liquid
may optionally be slightly heated, e. g. at a temperature between 25 and 65 "C, preferably 40
to 60°C (e. g. about 50°C).
In a preferred embodiment of the invention step (a) comprises the step of separating and
washing the iridium containing precipitate. Particularly preferably, the precipitate is
repeatedly washed, until halide ions (specifically chloride ions) can no longer be detected in
the filtrate. The detection of halide ions in the filtrate can be performed in a manner known to
the skilled person, for example using silver ions.
The detection of chloride ions as silver chloride precipitate is very sensitive. With the naked

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eye chloride ions down to an amount of 50 ppm can be detected, i. e. the absence of turbidity
when adding silver ions typically indicates a chloride content of less than about 50 ppm.
Reprecipitation may optionally be conducted by dissolving the iridium containing precipitate
in a suitable solvent and again precipitating with the alkaline compound (as described
above). As solvents e. g. organic (e. g. acetic acid) or inorganic acids (e. g. hydrochloric acid,
nitric acid) optionally in admixture with a protic solvent, as defined above, may be used.
When desired, the reprecipitation may also be conducted in the presence of at least one
compound selected from component (i). This is preferred. The reprecipitation step may
optionally be conducted once or several times (e. g. twice, thrice). Preferably, the
reprecipitation step(s) is (are) conducted in an atmosphere of inert gas (as described above).
Typically, precipitates are obtained in step (a), that surprisingly even without conducting any
reprecipitation step exhibit a high purity, as subsequently described in detail with regard to
the obtained precipitate. Thus, a more preferred embodiment does not include a
reprecipitation step of the iridium containing precipitate.
The optional steps of separating, washing and reprecipitating the precipitate are preferably
conducted in an atmosphere of inert gas.
The iridium containing precipitate obtained in step (a) may be obtained in very good yields
of typically about 92 to 95% or more, based on iridium (i. e moles Ir (educt)/moles Ir
(product)).
In one embodiment, step (a) comprises a step of allowing the iridium containing precipitate
to age. The term "ageing" is known in the art and means a change in the physical and/or
chemical properties of a substance during storage. The changes may occur naturally (e. g. by
action of the ambient conditions on the substance) or may be generated artificially, e. g. by
action of elevated temperature.
In the present invention, however, it is not preferred to allow the iridium containing
precipitate to age. Rather, a freshly precipitated iridium containing precipitate is preferably
used for further reaction (e. g. the reaction in step (b)). The term "freshly precipitated" is to
be understood in such a way, that the exposure to conditions causing a change in chemical
and physical properties of the precipitate (i. e. allowing the precipitate to age) is preferably
prevented. Such conditions may for example be one or more conditions selected from
allowing to stand for a prolonged period of time (e. g. several hours, particularly more than 3

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hours), action of oxygen (for example in the form of air), removal of the protic solvent,
removal of hydrate water and the like.
In a particularly preferred embodiment one or more conditions selected from allowing to
stand for more than 3 hours (particularly for more than 2 hours, more preferably for more
than 1 hour, even more preferably for more than 30 minutes) at room temperature in an
atmosphere of inert gas, action of oxygen (e. g. in the form of air, particularly for more than
30 minutes) and complete drying are avoided. In this preferred embodiment the term freshly
precipitated refers to the precipitate obtained under such condition(s).
In this embodiment the precipitate obtained in step (a) is optionally reprecipitated, optionally
separated and optionally washed, as described above, and immediately used for the desired
application, e. g. for the reaction in step (b). The precipitate is preferably used for the desired
application within a period of time of less than 3 hours, more preferably within a period of
time of 2 hours, even more preferably within a period of time of 1 hour and most preferably
within a period of time of 30 minutes, measured from the time of separation from the
reaction mixture.
Step (b)
Step (b) comprises the reaction of the iridium containing precipitate obtained in step (a) to
give an iridium acetate containing solution.
According to the present invention step (b) is conducted in the presence of at least one
compound selected from oxalic acid, a salt of oxalic acid, formic acid and a salt of formic
acid (i. e. component (i)) and in the presence of at least one compound selected from (ii)
acetic acid (CH3CO2H) and/or acetic acid anhydride (CH3(CO)O(CO)CH3) (i. e. component
(ii)).
The salts of oxalic acid and formic acid are not particularly limited. Basically, any salt of
oxalic acid and any salt of formic acid may be used in step (b). Usually, the salt will be
selected so that it is soluble in the reaction mixture under the chosen reaction conditions.
Suitable examples of the salts of oxalic acid and suitable examples of the salts of formic acid
include but are not limited to the compounds exemplified for step (a).
The compound(s) selected from component (i) used in step (b) may be the same
compound(s) as in step (a). Alternatively, different compounds or different mixtures of
compounds selected from component (i) may be used in steps (a) and (b).

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Step (b) is preferably conducted in the presence of formic acid or a salt thereof.
According to the present invention step (b) is conducted in the presence of at least one
compound selected from CH3CO2H and/or CH3(CO)O(CO)CH3 (component (ii)). Preferably,
step (b) is conducted in the presence of CH3CO2H or in the presence of a mixture of
CH3CO2H and CH3(CO)O(CO)CH3, particularly preferably in the presence of CH3CO2H.
Component (ii) may be provided for the reaction in step (b) in any form. For example,
component (ii) may be present as such as well as in the form of a mixture with one or more
protic solvents. In a preferred embodiment component (ii) is used as such, i. e. without
addition of a protic solvent. Suitable protic solvents include the examples listed in step (a),
with water being preferred as protic solvent. The mixing ratio of component (ii) and the
protic solvent may be in the range of 99:1 to 1:99. As an example of one such mixture e. g. a
mixture of glacial acetic acid and water in a ratio of 10:90 to 50:50, in terms of volume parts,
may be illustrated. If component (ii) is provided as mixture with a protic solvent (mixture),
the protic solvents used in steps (a) and (b) may be the same or different. Preferably in both
steps the same protic solvent (mixture) is used. The use of component (ii) in the form of a
mixture with a protic solvent selected from water and a C1-C6 alkanol, as defined in step (a),
has proven useful.
In a particularly preferred embodiment step (b) is conducted in the presence of 100% by
weight to 95%by weight acetic acid (in water).
In step (b) the at least one compound selected from component (i) is preferably used in at
least an about equimolar amount (e. g. at least 0.8 mol equivalents, more preferably at least
1.0 mol equivalent, even more preferably 1.05 to 1.5 mol equivalents, based on iridium).
When a mixture of compounds of component (i) is used, the amounts shown refer to the total
number of moles of the selected compounds.
In step (b) the least one compound selected from component (ii) is used in a molar ratio of
the compound selected from component (ii) to iridium, that is significantly higher than the
stoichiometric ratio. Thus the at least one compound selected from component (ii) may serve
both as a reactant and as a solvent for the resulting iridium acetate.
In the course of the reaction in step (b) the reaction mixture is converted from a suspension
of the iridium containing precipitate to a solution of iridium acetate.
Accordingly, the reaction time for step (b) is chosen so that at the end of the reaction time an

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essentially clear solution containing no substantial (preferably no visible) amounts of solids
is formed. Preferred reaction times for step (b) are about 8 to about 50 hours, preferably
about 10 to about 25 hours, more preferably about 12 to about 17 hours.
In a preferred embodiment step (b) is conducted with heating e. g. at a temperature ranging
from about 80 to 120 °C, particularly preferably from about 90 to 105 °C.
It is particularly preferred to perform step (b) with heating to reflux. The exact temperature
will mainly depend upon the compound selected from component (ii), that will be used.
Typically a suitable temperature will be more than about 100 °C, e. g. about 101 to about 112
°C for 60% by weight acetic acid in water, about 118 °C for 100% by weight acetic acid
(glacial acetic acid) and about 139 °C for 100% by weight acetic anhydride.
Step (b) is preferably conducted in an atmosphere of inert gas.
Optionally, the solution obtained in step (b) comprising indium acetate may be filtered to
remove any insoluble residues possibly contained in the solution. However, usually no
visible residue is seen on the filter, which is indicative for the completeness of the reaction in
step (b). The optional filtering step may be performed by means known to one of ordinary
skill in the art, e. g. by filtering through various filters (e. g. Blauband, or membrane) or/and
polishing, filtration through various filters (e. g. nylon filters having a pore size of preferably
more than 5 μm to 20 μm).
The filtration may also be performed under pressure, for example under pressures between 1
and 5 bar, preferably at about 2 bar. The filtration may be performed at any temperature, e. g.
at a temperature ranging from 20 to 30 °C. The filtration may be performed in the absence or
presence of filtering aids, such as glass frost, activated carbon, cellulose (e. g. Hyflow). The
filtration is preferably conducted in an atmosphere of inert gas.
If step (b) is conducted with heating, it is preferable to cool or allow to cool the solution to
room temperature prior to performing optional steps, such as filtration or step (c).
Step (c)
If desired the indium acetate may be isolated from the solution as a solid. The separation
may be performed in a per se known manner, e. g. by concentrating the reaction mixture or
distilling off the volatile components contained in the reaction mixture optionally under
vacuum and/or at elevated temperatures. However, the present invention is not limited to

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these illustrated methods of isolation. Step (c) may be conducted in an atmosphere of inert
gas, however, this is neither required nor preferred.
In the process of the present invention iridium acetate can be produced in very good yields
(about 95% or more, based on Iridium (in moles) and with respect of the entire process).
Additionally the iridium acetate of the present invention is characterized by its high purity, as
described in the following in more detail.
Iridium acetate
In one embodiment, the present invention relates to iridium acetate obtainable according to
the process as described in any of claims 18 to 22.
After conducting the steps (a) and (b) of the present invention a solution containing iridium
acetate is obtained. In one embodiment, the present invention relates to a such a solution
containing iridium acetate.
As described above, iridium acetate may also be isolated from the solution as a solid, if
desired. In another embodiment, the present invention relates to iridium acetate as a solid.
Hence, according to the present invention, the iridium acetate of the present invention may
be present as a solid or dissolved in a suitable solvent. Suitable solvents include, but are not
limited to protic solvents. Suitable protic solvents are, for example, water and alcohols, e. g.
C1-C6 alkanols (preferably methanol, ethanol, n-propanol, iso-propanol, n-butanol, sec-
butanol, tert-butanol), and mixtures of two or more of these solvents. If the iridium acetate is
present as a solution this solution is not limited with regard to its composition.
A preferred solution comprises (preferably consists of), in addition to the iridium acetate of
the present invention, at least one compound selected from component (i), and at least one
compound selected from component (ii), and, optionally, a protic solvent (mixture). This
preferred solution is not limited with regard to its composition.
In a more preferred embodiment the iridium acetate solution comprises (preferably consists
of) the following components:
- 2 to 20% by weight of iridium acetate,
20 to 90% by weight of component (ii) (preferably acetic acid),

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1 to 20% by weight of component (i) (preferably formic acid), and
5 to 70% by weight of a protic solvent (mixture) (preferably water).
The iridium acetate of the present invention (as a solid and as a solution) is characterized by
its low content of impurities. Such impurities may for example be ionic constituents
contained in the starting compounds used, such as ammonium, alkali or alkaline earth ions or
halide ions.
The iridium acetate of the present invention is in the form of a solution as well as in form of
the isolated solid stable towards air and may be stored for a prolonged period of time (e. g.
for a period of several months to 2 years) without any change in the physical and chemical
properties.
Moreover, the iridium acetate present as a solid is characterized by its very good solubility in
solvents, such as water, acetic acid (CH3COOH) and methanol, and mixtures of one or more
of these solvents.
Typically, the iridium acetate of the present invention (as solid and as a solution) is blue-
green in color, whereas prior art consistently reports "green iridium acetate". In all examples
of EP-A-01 046 629 a dark green solution or suspension of iridium acetate is obtained, from
which a dark green solid is obtained by evaporation. The solution of iridium acetate obtained
in example 1 of WO-A-96/23757 is also described as being "green".
Figure 1 shows a visible/ultraviolet spectrum of the compound obtained in comparative
example 1 (according to EP-A-01 046 629).
Figure 2 shows a visible/ultraviolet spectrum of iridium acetate according to the present
invention.
A comparison of the spectra shown in Figure 1 and Figure 2 shows that the absorption
maximum (λmax) of the iridium acetate of the present invention is shifted towards shorter
wavelengths, as compared to the iridium acetate obtained according to the process of EP-A-
01 046 629. This indicates a specific chemical structure of the iridium acetate of the present
invention. Generally, the absorption maximum (λ.max) of the iridium acetate of the present
invention is shifted to wavelengths shorter than 680 nm, preferably shorter than 675 nm and
more preferably shorter than 670 nm in the visible/ultraviolet spectrum.
In another aspect, the present invention relates to an iridium acetate (as a solid or as a

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solution, as described above) characterized in having a low halide (preferably chloride)
content. In particular, the iridium acetate of the present invention is characterized by having a
very low halide (preferably chloride) content of less than 1000 ppm, and more preferably less
than 800 ppm (all ppm values in terms of parts by weight, based on Ir)
In particularly preferred embodiments of the invention, as described above, halide contents
below 200 ppm, particularly below 100 ppm or even lower, e. g. below 50 ppm, are obtained
(all ppm values in terms of ppm by weight, based on Ir).
The content of other impurities (particularly ammonium, alkali or alkaline earth ions) is in
the same order of magnitude as the results obtained for the halide impurities.
In preferred embodiments, the contents of other impurities, particularly ammonium, alkali
(i. e. Li, Na, K, Rb, Cs, preferably K) or alkaline earth (i. e. Mg, Ca, Ba, Sr, preferably Mg
and Ca) ions each are typically below 1000 ppm, preferably below 500 ppm and particularly
preferably below 300 ppm (based on Ir).
The halide content (which in this application is understood as being the total halide content,
comprising the ionically as well as the covalently bound halide of the sample) may be
determined using methods known to one of ordinary skill in the art. In the present invention a
preferably used method of the determination (in the intermediate and in the end product) is
the so called "analysis of total halide content according to W1CKBOLD", as described in the
examples.
The determination of the content of other possible ionic constituents (in the intermediate and
in the end product) (such as ammonium, alkali or alkaline earth ions) is also known to one of
ordinary skill in the art and, for example, ICP analysis (ICP = Inductive Coupled Plasma)
may be used.
In a preferred embodiment, the iridium acetate with a low halide content of the present
invention can be obtained by the processes defined in any of claims 18 to 22.
Iridium Containing Precipitate
In another aspect, the present invention also relates to an iridium containing precipitate.
The term "iridium containing precipitate", as used herein, refers to the iridium containing
precipitate obtainable in step (a) from the iridium compound by adding the alkaline

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compound (i. c. in the presence of OH~-ions) and is to be understood in this broad sense.
Without wishing to be bound by any specific theory it is believed that the precipitate is an
indium oxygen compound having besides the iridium atoms as compound constituents one or
more compound constituents, selected from hydroxo, oxo and aquo groups and hydrate
constituents, wherein the iridium atoms may be present in only one oxidation state (e. g. all
in (+III) corresponding to Ir(III) oxide hydrate, or all in (+IV) corresponding to Ir(lV) oxide
hydrate) or the iridium atoms may be present in oxidation states differing from one another.
e. g. a portion in the oxidation state (+III) and the remainder in the oxidation state (+IV).
Anyone skilled in the art of transition metal oxygen compounds knows that typically such
compounds are non stoichiometric compounds.
In a preferred embodiment the term "iridium containing precipitate" refers to the freshly
precipitated precipitate, as described above.
The iridium containing precipitate obtainable by conducting step (a) is characterized by a
good filterability.
Additionally, it was surprisingly found that by conducting step (a) in the presence of at least
one compound selected from component (i) a precipitate may be obtained, that is
characterized by a very good solubility for example in inorganic acids, such as mineral acid
(e. g. hydrochloric acid or nitric acid), and organic acids, such as acetic acid (or acetic
anhydride).
Typically, the precipitate can be completely (typically more than 95% by weight) dissolved
in the aforesaid acids or a mixture thereof. The role that the presence of component (i) plays
is still unclear, however, it seems to cause the good solubility. The very good solubility of
the iridium containing precipitate according to the present invention also means an
improvement of the yield and hence of the productivity of the process for the preparation of
iridium acetate. By minimizing the insoluble impurities the purity and stability of the indium
acetate obtained in step (b) is improved significantly.
In one embodiment the iridium containing precipitate is obtainable by the process according
to any of claims 9 to 17.
According to the present invention, the iridium containing precipitate of the present
invention is characterized in particular by its low content of impurities.

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Such impurities may for example be ionic constituents contained in the starting compounds
used, such as ammonium, alkali or alkaline earth ions or halide ions. For a later use as a
catalyst or catalyst precursor, particularly the presence of halide ions (e. g. chloride, bromide
or iodide ions, particularly chloride ions) is undesirable.
Hence, in a preferred embodiment the invention relates to an iridium containing precipitate
having a low halide (preferably chloride) content.
The iridium containing precipitate of the present invention is characterized by a very low
halide content (particularly chloride content). Typically the halide content is below 1000
ppm and more preferably below 800 ppm (based on Ir).
In particularly preferred embodiments of the invention, as described above, halide contents
below 200 ppm, particularly below 100 ppm or even lower, e. g. below 50 ppm, are typically
obtained. The given ppm values are based on iridium (in terms of parts by weight).
The precipitate is characterized by a very high purity in other respects as well. The content of
other impurities is in the same order of magnitude as the results obtained for the halide
impurities. Such other impurities may for example be ionic constituents contained in the
starting compounds used, such as ammonium, alkali or alkaline earth ions.
The content of other impurities, particularly ammonium, alkali (i. e. Li, Na, K, Rb, Cs,
preferably K) or alkaline earth (i. e. Mg, Ca, Ba, Sr, preferably Mg and Ca) ions is typically
below 1000 ppm, preferably below 500 ppm and particularly preferably below 300 ppm
(based on Ir).
The iridium containing precipitate having a low total halide content of the present invention
can, for example, be obtained as an intermediate by the process as described in any of claims
9 to 17 .
Surprisingly, these high degrees of purity in the products and intermediates of the present
invention are obtained even when, as preferred in the present invention, troublesome means
to reduce undesired impurities (particularly halide), as taught in the prior art (such as
reprecipitation of the iridium containing precipitate e. g. by dissolving in nitric acid or a
mixture of nitric acid and hydrogen peroxide and again precipitating by adding an alkali
metal hydroxide, carbonate or hydrogen carbonate according to EP-A-1046629), are omitted.
The fact that the products and intermediates of the process of the present invention (i.e.,

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iridium acetate and iridium containing precipitate) obtainable in absence of a reprccipitation
step, according to a preferred embodiment of the invention, has even lower halide content
than the iridium product obtainable according to the prior art process including such
reprecipitation step (here a halide content of about 6% is obtained, in terms of % by weight
based on Ir) is particularly surprising.
Uses
The present invention also relates to the use of the iridium acetate of the present invention (as
a solid or in solution) and to the use of the iridium containing precipitate of the present
invention as a catalyst or as a catalyst precursor in homogeneously or heterogeneously
catalyzed reactions.
Preferably, the catalyzed reactions are reactions, selected from the group consisting of
carbonylation reactions, hydroforrnylation reactions, coupling reactions, oxidation reactions,
hydrogenation reactions, hydrosilylation reactions and isornerization reactions, preferably
carbonylation reactions.
A particularly preferred embodiment relates to the use as a catalyst or as a catalyst precursor
in homogeneously catalyzed reactions, particularly carbonylation reactions. Preferred
carbonylation reactions include the carbonylation of methanol into acetic acid.
The iridium acetate of the present invention (as a solid or in solution) and the iridium
containing solid of the present invention may also be used in electroplating and for the
preparation of catalysts for heterogeneous catalysis.
In preferred embodiments, the present invention relates to the following items:
1. A process for the preparation of an iridium containing precipitate, the process
comprising:
(a) reacting an iridium compound with an alkaline compound in a protic solvent to
obtain an iridium containing precipitate, wherein the reaction is conducted in the
presence of at least one compound selected from oxalic acid, a salt of oxalic acid,
formic acid and a salt of formic acid.
2. The process according to item 1, wherein the iridium compound is an iridium halogen
compound.

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3. The process according to item 1 or 2, wherein step (a) comprises separating the
obtained precipitate from the reaction mixture.
4. The process according to item 3, further comprising washing of the separated
precipitate.
5. The process according to item 4, wherein washing is conducted until the washing
liquid is free of halide ions.
6. The process according to any one of items 1 to 5, wherein the reaction in step (a) is
conducted with heating.
7. The process according to any one of items 1 to 6, wherein the alkaline compound is
selected from ammonium, alkali and alkaline earth hydroxides, carbonates and
hydrogen carbonates and amines of the formula NR1R2R3, wherein R1, R2 and R3 are
independently selected from a hydrogen atom and C1-C6 alkyl groups, and mixtures
thereof.
8. A process for the preparation of iridium acetate comprising the steps of:

(a) reacting an iridium compound with an alkaline compound in a protic solvent to
obtain a precipitate according to any one of items 1 to 7,
(b) reacting the iridium containing precipitate in the presence of
(i) at least one component selected from oxalic acid, a salt of oxalic acid,
formic acid and a salt of formic acid, and
(ii) at least one compound selected from CH3CO2H and CH3(CO)O(CO)CH3
to give an iridium acetate containing solution.
9. The process according to item 8, further comprising:
(c) isolating the iridium acetate as a solid from the solution.
10. The process according to any one of items 8 or 9, wherein step (b) is conducted with
heating.
11. The process according to any one of items 1 to 10, wherein the oxalic acid salt and/or
the formic acid salt in steps (a) and (b) are independently selected from ammonium,
alkali metal and alkaline earth metal salts.
12. The process according to any one of items 1 to 11, wherein the protic solvent used in

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steps (a) and/or (b) is independently selected from water, a C1-C6, alkanol and mixtures
thereof.
13. The process according to any one of items 8 to 12, wherein the iridium containing
precipitate used in step (b) is a freshly precipitated precipitate.
14. Iridium acetate as a solid, obtainable according to any one of items 9 to 13.
15. A solution, containing iridium acetate, obtainable according to any one of items 8 to
13.
16. A solution comprising (A) iridium acetate, (B) at least one compound selected from
oxalic acid, a salt of oxalic acid, formic acid and a salt of formic acid, (C) at least one
compound selected from CH3CO2H and CH3(CO)O(CO)CH3 and (D) optionally a
protic solvent.
17. An iridium containing precipitate, obtainable according to the process according to any
one of items 1 to 7.
18. Use of an iridium acetate, according to item 14 or of a solution according to item 15 or
16 or of a precipitate according to item 17 as a catalyst or as a catalyst precursor in
homogeneously or heterogeneously catalyzed reactions, selected from carbonylation
reactions, hydroformylation reactions, coupling reactions, oxidation reactions,
hydrogenation reactions, and hydrosilylation reactions.
19. Use of a solid according to item 14 or of a solution according to item 15 or 16 or of a
precipitate according to item 17 in electroplating.

20. Use of a solid according to item 14 or of a solution according to item 15 or 16 or of a
precipitate according to item 17 for the preparation of catalysts for the heterogeneous
catalysis.
21. A process as defined in any of items 1 to 7 for the preparation of an iridium
containing precipitate having a low halide content.
22. The process according to item 21, wherein the iridium compound is an iridium
chlorine compound.

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23. The process according to item 21 or 22, wherein step (a) further comprises separating
the obtained precipitate from the reaction mixture.
24. The process according to item 21 or 22, wherein step (a) further comprises washing
of the separated precipitate until the halide content is less than 1000 pprn, preferably
until the halide content is less than 800 ppm (based on Ir).
25. A process as defined in any of items 1 to 13 and 21 to 24 for the preparation of
iridium acetate having a low halide content.
26. An iridium acetate, characterized in having a halide content of less than 1000 pprn,
preferably less than 800 ppm (based on Ir).
27. The iridium acetate according to item 26, characterized in having a content of
ammonium ions, alkali ions (i. e. Li, Na, K, Rb, Cs) or alkaline earth ions (i. e. Mg,
Ca, Ba, Sr), respectively, below 1000 ppm, preferably below 500 ppm and
particularly preferably below 300 ppm (based on Ir).
28. The iridium acetate according to item 26 or 27, characterized in having an absorption
maximum (λmax) at wavelengths shorter than 680 nm, preferably shorter than 675 nm
and more preferably shorter than 670 nm in the visible/ultraviolet spectrum.
29. The iridium acetate according to any one of items 26 to 28, wherein the iridium
acetate is a solid.
30. A solution comprising iridium acetate according to any one of items 26 to 29 and a
suitable solvent.
31. The solution according to item 30, wherein the solvent is a protic solvent.
32. The solution according to item 30 or 31, further comprising:
(i) at least one compound selected from the group consisting of oxalic acid, a salt of
oxalic acid, formic acid and a salt of formic acid, and
(ii) at least one compound selected from CH3COOH and CH3(CO)O(CO)CH3.
33. An iridium containing precipitate, characterized in having a halide content of less
than 1000 ppm, preferably less than 800 ppm (based on Ir).

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34. Use of iridium acetate according to any one of items 26 to 29 or of a solution
according to any one of items 30 to 32 or of a precipitate according to item 33 as a
catalyst or as a catalyst precursor in homogeneously or heterogeneously catalyzed
reactions, selected from carbonylation reactions, hydroformylation reactions,
coupling reactions, oxidation reactions, hydrogenation reactions, and hydrosilylation
reactions.
35. Use of iridium acetate according to any one of items 26 to 29 or of a solution
according to any one of items 30 to 32 or of a precipitate according to item 33 in
galvanotechnics or for the preparation of catalysts for the heterogeneous catalysis.
Examples
The following examples serve to further explain the invention and are not to be construed as
limiting. In the present invention "water" is understood as being water in its deionised form
("DI water").
Measuring Methods/Analytics
Visible/Ultraviolet Spectra:
Measurement of the visible/ultraviolet spectra was conducted at room temperature using a
UV spectrometer "Jena Specord 200" (tungsten lamp (VIS), deuterium lamp (UV)) and 1 cm
cuvets (quartz glass cuvets "Soprasil", manufactured by Helma) in a measuring range of 200
nm to 1100 nm. Solid iridium acetate was dissolved in DI water in the concentrations
indicated in Figures 1 and 2.
Determination of the Halide Content:
The determination of the halide (preferably chloride) content was conducted according to a
method comprising the steps: (1) taking up the sample in a suitable solvent, (2) combustion
in a oxyhydrogen flame, (3) collecting the condensate in a solution of sodium hydroxide and
(4) determination of the halide content by ion chromatography (IC). This method is known
by the designation "analysis of total halide content according to WICKBOLD".

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Determination of the Content of Alkali Ions and Iridium:
The determination of the iridium content and of the content of any optionally contained alkali
ions was conducted by ICP analysis in a manner known to one of ordinary skill in the art.
Example 1
Preparation of an Iridium Containing Precipitate (Step (a))
Apparatus: 1-L standard stirring apparatus (condenser, mechanical stirrer, inert)
With stirring 50 g of iridium as ca. 4% by weight solution of H2IrCl6 were heated to about 95
°C with 4.0 g of oxalic acid and maintained at that temperature for about 2 hours. After
addition of KOH (10% by weight in water, about 10 eq. based on Ir) within 20 minutes the
reaction mixture was allowed to cool to room temperature. The pH was readjusted with
acetic acid (50% by weight in water) to a value of approximately 7.5. Filtration through
Blauband at room temperature and subsequent washing of the suspension with acetic acid
(10% by weight in water) and DI water until the washing water was free of chlorine gave the
product as a compact black solid.
An analysis of the filtrate by ion chromatography gave an iridium content of yield based on iridium contained in the filter cake was > 99 %.
Example 2
Preparation of Iridium Acetate (Step (b))
Apparatus: 500-rnL standard stirring apparatus (condenser, mechanical stirrer, inert)
The filter cake obtained in step (a) together with 200 g of glacial acetic acid was placed in
the apparatus and 2 g of formic acid were added. With stirring the reaction mixture was
heated to reflux. At this temperature the reaction mixture was allowed to dissolve for 10
hours. After cooling to room temperature and filtration through Blauband the product was
obtained as dark blue green solution. Removal of the solvent under vacuum yielded solid Ir-
acetate as dark green crystals (yield: ca. 78-80%, based on iridium).

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An analysis of the solution obtained in step (b) gave the following results: Cl 50 ppm, Ir ca. 2.5-3% by weight.
The visible/ultraviolet spectrum of the product shows an absorption maximum at λmax =
668.4 nm (cf. Figure 2). The concentration of iridium acetate in DI water is 51,9 mg/50 ml
(= 1,038 mg/ml).
Example 3
Example 1 was repeated with the sole difference that in step (a) 50 g of iridium as ca. 4% by
weight solution of H2lrCl6 were heated to about 95°C with 4.0 g of oxalic acid and
maintained at that temperature for about 90 minutes.
Step (b) was performed as described with respect to Example 2, whereby solid indium
acetate is obtained as dark green crystals (yield: 78 - 80%, based on iridium). The iridium
acetate obtained is dissolved in DI water. The concentration of the solution obtained was
3,53 % by weight of Ir.
Analytical Results
a) total chlorine content according to WICKBOLD:
Cl content (based on the solution): Cl = 28 ppm
Cl content (based on the Ir content): Cl = 793 ppm
b) potassium content using ICP:
K content (based on the solution) K K content (based on the Ir content) K The visible/ultraviolet spectrum of the product shows an absorption maximum at λmax -
668.4 nm.

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Example 4
Preparation of an Iridium Containing Precipitate (Step (a))
Apparatus: 1-L standard stirring apparatus (condenser, mechanical stirrer, inert)
With stirring 50 g of iridium as ca. 4% by weight solution of H2lrCl6 were heated to about
98°C with 4.0 g of oxalic acid and maintained at that temperature for about 90 minutes. After
addition of KOH (10% by weight in water, about 10 eq. based on Ir) within 20 minutes the
reaction mixture was allowed to cool to room temperature. The pH was readjusted with
acetic acid (50% by weight in water) to a value of approximately 7.5. Filtration through
Blauband at room temperature and subsequent washing of the suspension with acetic acid
(10% by weight in water) and DI water until the washing water was free of chlorine gave the
product as a compact black solid.
An analysis of the filtrate by ion chromatography gave an iridium content of yield based on iridium contained in the filter cake was > 99 %.
Preparation of Iridium Acetate (Step (b))
Apparatus: 500-mL standard stirring apparatus (condenser, mechanical stirrer, inert)
The filter cake obtained in step (a) together with 200 g of glacial acetic acid was placed in
the apparatus and 2 g of formic acid were added. With stirring the reaction mixture was
heated to reflux. At this temperature the reaction mixture was allowed to dissolve for 12
hours. After cooling to room temperature and filtration through Blauband the product was
obtained as dark blue green solution. Removal of the solvent under vacuum yielded solid Ir-
acetate as dark green crystals (yield: ca. 78%, based on iridium). The iridium acetate
obtained is dissolved in DI water. The concentration of the solution was 4,06% by weight of
Ir.
Analytical Results
a) total chlorine content according to WICKBOLD:
Cl content (based on the solution): Cl - 30 pprn
Cl content (based on the Ir content): CI = 739 ppm

WO 2006/125628 PCT/EP2006/004964
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The visible/ultraviolet spectrum of the product shows an absorption maximum at λmax =
668.2 nm. The concentration of iridium acetate in DI water is 0,744 mg/ml.
Comparative example
(According to EP 1 046 629, Example 2)
Apparatus: 100-mL standard stirring apparatus (condenser, stirrer), inert gas atmosphere
8.7 g of a ca. 23% by weight solution of H2IrCl6 were concentrated under vacuum at 55°C,
until a viscous oil was formed. A black solid resulted after cooling to room temperature. This
was taken up in 60 ml water and heated to 80°C. A dark solution formed, which was
dropwise adjusted to pH 7.3 with In KOH solution. Here a black precipitate formed which
was filtered still hot through Blauband. The filter cake was then washed with water using 100
ml portions until chlorine free. The filter cake was sucked dry. The resulting solid was
suspended with 60 ml glacial acetic acid and heated to reflux for 23 hours. 2 hours prior to
the end of the refluxing time further 15 ml of glacial acetic acid were added. After cooling to
room temperature the resulting dark green solution was fine filtered through a G4 glass frit.
After concentration of the solution under vacuum 2.5 g of a green solid (yield: 65%, based on
iridium) formed.
An analysis of the product by ion chromatography gave an iridium content of 56.6% by
weight (based on the solid).
Analytical Results
Total chlorine content according to WICKBOLD:
Cl content (based on the solid): Cl = 6% by weight (60000 ppm)
Cl content (based on Ir) Cl = 10.6% by weight (106000 ppm)
These values are markedly higher than the Cl contents of the iridium acetate of the present
invention.
The visible/ultraviolet spectrum of the product shows an absorption maximum at λmax = 682
nm (cf. Figure 1). The concentration of iridium acetate in DI water is 0,61 mg/ml.

WO 2006/125628 PCT/EP2006/004964
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Claims
1. An iridium acetate, characterized in having a halide content of less than 1000 ppm,
preferably less than 800 ppm (based on Ir).
2. The iridium acetate according to claim 1, characterized in having contents of
ammonium ions, alkali ions (i. e. Li, Na, K, Rb, Cs) or alkaline earth ions (i. e. Mg,
Ca, Ba, Sr), respectively, of each below 1000 ppm, preferably below 500 ppm and
particularly preferably below 300 ppm (based on lr).
3. The iridium acetate according to claim 1 or 2, characterized in having an absorption
maximum (λmax) at wavelengths shorter than 680 nra in the visible/ultraviolet
spectrum.
4. The iridium acetate according to any one of claims 1 to 3, wherein the iridium acetate
is a solid.
5. A solution comprising iridium acetate according to any one of claims 1 to 4 and a
suitable solvent.
6. The solution according to claim 5, wherein the solvent is a protic solvent.
7. The solution according to claim 5 or 6, further comprising:
(i) at least one compound selected from the group consisting of oxalic acid, a salt of
oxalic acid, formic acid and a salt of formic acid, and
(ii) at least one compound selected from CH3COOH and CH3(CO)O(CO)CH3.
8. An iridium containing precipitate, characterized in having a halide content of less
than 1000 ppm, preferably less than 800 ppm (based on Ir).
9. A process for the preparation of an iridium containing precipitate, the process
comprising:
(a) reacting an iridium compound with an alkaline compound in a protic solvent to
obtain an iridium containing precipitate, wherein the reaction is conducted in the
presence of at least one compound selected from oxalic acid, a salt of oxalic acid,
formic acid and a salt of formic acid.

WO 2006/125628 PCT/EP2006/004964
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10. The process according to claim 9, wherein the iridium compound is an iridium
halogen compound.
11. The process according to claim 10, wherein the iridium compound is an iridium
chloro compound.
12. The process according to any of claims 9 to 11, wherein step (a) comprises separating
the obtained precipitate from the reaction mixture.
13. The process according to claim 12, further comprising washing of the separated
precipitate.
14. The process according to claim 12, wherein step (a) further comprises washing of the
separated precipitate until the halide content is less than 1000 ppm, preferably until
the halide content is less than 800 ppm (based on Ir).
15. The process according to any of claims 13 or 14, wherein washing is conducted until
the washing liquid is free of halide ions.
16. The process according to any one of claims 9 to 15, wherein the reaction in step (a) is
conducted with heating.
17. The process according to any one of claims 9 to 16, wherein the alkaline compound is
selected from ammonium, alkali and alkaline earth hydroxides, carbonates and
hydrogen carbonates and amines of the formula NR!R2R3, wherein R1, R2 and R3 arc
independently selected from a hydrogen atom and Ci-Cfi alkyl groups, and mixtures
thereof.
18. A process for the preparation of iridium acetate comprising the steps of:

(a) reacting an iridium compound with an alkaline compound in a protic solvent to
obtain a precipitate according to any one of claims 9 to 17,
(b) reacting the iridium containing precipitate in the presence of
(i) at least one component selected from oxalic acid, a salt of oxalic acid,
formic acid and a salt of formic acid, and
(ii) at least one compound selected from CH3CO2H and CII3(CO)O(CO)CH3
to give an iridium acetate containing solution.
19. The process according to claim 18, further comprising:

WO 2006/125628 PCT/EP2006/004964
32
(c) isolating the iridium acetate as a solid from the solution.
20. The process according to any one of claims 18 or 19, wherein step (b) is conducted
with heating.
21. The process according to any one of claims 9 to 20, wherein the oxalic acid salt
and/or the formic acid salt in steps (a) and (b) are independently selected from
ammonium, alkali metal and alkaline earth metal salts.
22. The process according to any one of claims 9 to 21, wherein the protic solvent used in
steps (a) and/or (b) is independently selected from water, a C1-C6, alkanol and
mixtures thereof.
23. The process according to any one of claims 18 to 22, wherein the indium containing
precipitate used in step (b) is a freshly precipitated precipitate.
24. Use of iridium acetate according to any one of claims 1 to 4 or of a solution
according to any one of claims 5 to 7 or of a precipitate according to claim 8 as a
catalyst or as a catalyst precursor in homogeneously or heterogeneously catalyzed
reactions, selected from carbonylation reactions, hydroformylation reactions,
coupling reactions, oxidation reactions, hydrogenation reactions, and hydrosilylation
reactions.
25. Use of iridium acetate according to any one of claims 1 to 4 or of a solution
according to any one of claims 5 to 7 or of a precipitate according to claim 8 in
electroplating or for the preparation of catalysts for heterogeneous catalysis.

The present invention relates to a process or the preparation of indium acetate
comprising the steps (a) reacting an indium compound with an alkaline compound in a
protic solvent to obtain an iridium containing precipitate, where the reaction is
conducted in the presence of at least one component (i) selected from oxalic acid, a slat
of oxalic acid, a salt of oxalic acid, formic acid and a salt of formic acid, (b) reacting the
precipitate in the presence of at least (i) one compound selected from oxalic acid, a salt
of oxatic acid, formic acid and a salt of formic acid, and (ii) CH3CH2H and/or CH3(CO)O(CO)CH3 to give an iridium acetate containing solution. The invention also relates to indium acetate having a low halide content, to an indium containing
precipitate and to uses of the iridium containing precipitate of the present invention and the iridium acetate of the present invention.

Documents:

04515-kolnp-2007-abstract.pdf

04515-kolnp-2007-claims.pdf

04515-kolnp-2007-correspondence others.pdf

04515-kolnp-2007-description complete.pdf

04515-kolnp-2007-drawings.pdf

04515-kolnp-2007-form 1.pdf

04515-kolnp-2007-form 2.pdf

04515-kolnp-2007-form 3.pdf

04515-kolnp-2007-form 5.pdf

04515-kolnp-2007-international publication.pdf

04515-kolnp-2007-international search report.pdf

04515-kolnp-2007-pct request form.pdf

4515-KOLNP-2007-(08-10-2014)-CORRESPONDENCE.pdf

4515-KOLNP-2007-(08-10-2014)-FORM-1.pdf

4515-KOLNP-2007-(15-03-2013)-ABSTRACT.pdf

4515-KOLNP-2007-(15-03-2013)-CLAIMS.pdf

4515-KOLNP-2007-(15-03-2013)-CORRESPONDENCE.pdf

4515-KOLNP-2007-(15-03-2013)-DESCRIPTION (COMPLETE).pdf

4515-KOLNP-2007-(15-03-2013)-DRAWINGS.pdf

4515-KOLNP-2007-(15-03-2013)-FORM 1.pdf

4515-KOLNP-2007-(15-03-2013)-FORM 2.pdf

4515-KOLNP-2007-(15-03-2013)-FORM 3.pdf

4515-KOLNP-2007-(15-03-2013)-OTHERS.pdf

4515-KOLNP-2007-(15-03-2013)-PETITION UNDER RULE 137.pdf

4515-KOLNP-2007-(17-11-2014)-PETITION UNDER RULE-137.pdf

4515-KOLNP-2007-(18-09-2014)-CORRESPONDENCE.pdf

4515-KOLNP-2007-CORRESPONDENCE 1.1.pdf

4515-KOLNP-2007-CORRESPONDENCE OTHERS 1.2.pdf

4515-KOLNP-2007-CORRESPONDENCE OTHERS 1.3.pdf

4515-kolnp-2007-form 18.pdf

4515-KOLNP-2007-OTHERS.pdf

4515-KOLNP-2007-PA.pdf

4515-KOLNP-2007-PRIORITY DOCUMENT.pdf


Patent Number 263866
Indian Patent Application Number 4515/KOLNP/2007
PG Journal Number 48/2014
Publication Date 28-Nov-2014
Grant Date 25-Nov-2014
Date of Filing 23-Nov-2007
Name of Patentee UMICORE AG & CO. KG
Applicant Address RODENBACHER CHAUSSEE 4, 63457 HANA-WOLFGANG
Inventors:
# Inventor's Name Inventor's Address
1 KAYSER, BERND KARLSTRASSE 114 80335 MUNCHEN
2 KARCH, RALF KATHE-KOLLWITZ-STR. 24 63801 KLEINOSTHEIM
3 RIVAS-NASS, ANDREAS AM HUNDACKER 10 55257 BUDENHEIM
4 WIDMER, JURGEN BODO HEIDELBERGER STRASSE 27A 64285 DARMSTADT
5 WINDE, ROLAND HUEHNERWEG 18 60599 FRANKFURT
6 WORNER, EILEEN EIFEISTRASSE 11 63477 MAINTAL
PCT International Classification Number C07C 53/10
PCT International Application Number PCT/EP2006/004964
PCT International Filing date 2006-05-24
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10 2005 027 954.6 2005-06-16 Germany
2 10 2005 024 116.6 2005-05-25 Germany