Title of Invention

DIENE-BIS-AQUO-RHODUJM(I) COMPLEXES AND A PROCESS FOR PREPARING THE SAME

Abstract Diene-bis-aquo-rhodium(I) complex of the formula: [Rh(diene)(H2O)2]X (I) where diene is a cyclic diene and X is a noncoordinating anion.
Full Text

Diene-Bis-Aquo-Rhodium(I) complexes, process for preparing them and their use
The present invention relates to diene-bis-aquo-rhodium(I) complexes, a process for
preparing them and their use in catalytic reactions and for preparing heterogeneous catalysts.

More than 80% of industrially produced chemicals are produced with the aid of catalytic
processes. Catalytic processes are generally more economical and environmentally friendly
than corresponding stoichiometric organic reactions.
In homogeneously catalyzed processes using metal compounds as homogeneous catalysts,
the wide range of applications of the catalysts requires a wide range of possible ligand
systems. Thus an optimum choice from among a wide variety of ligand systems is necessary
to achieve high yields and selectivities in homogeneously catalyzed processes, which at the
same time also increases the need for universally usable precursor metal compounds. The
need for continual improvement of the catalyst systems and the processes for preparing them
is therefore clear.
The majority of the homogeneously catalyzed processes and reactions described in the prior
art are concerned with symmetric and asymmetric hydrogenation reactions of unsaturated
C-C, C-O, C-S and C-N bonds. Precursor metal compounds for such reactions of great
industrial interest are provided, for example, by monomeric and polymeric ruthenium(II)
complexes or mononuclear or binuclear rhodium(I)-olefin complexes.
Rhodium(I)-olefin complexes are widely used as, for example, catalysts in symmetric and
asymmetric hydrogenation reactions, in hydroformylations, hydrosilylations and coupling
reactions. Numerous rhodium(I)-olefin complexes are known in this field of technology, as


described, for example, in Houben-Weyl "Methoden der organischen Chemie" (4th Edition,
Vol. XIII/9b, "Metallorganische Verbindungen")- All these known complexes have olefinic
units which coordinate to the rhodium and stabilize the metal in its respective oxidation
state.
Typical olefins present in such complexes are, for example, 1,5-cyclooctadiene (COD), 1,3-
cyclooctadiene, norbomadiene (NBD), cyclooctatriene, butadiene, various alkylated and/or
substituted butadiene derivatives and ethylene. One of the most frequently used dienes is 1,5-
cyclooctadiene (COD).
Since the rhodium in the abovementioned complexes always has the formal oxidation state
+1, anionic counterions are always necessarily present. Among these anions, a distinction
can be made between those which are coordinated to the rhodium, for example halides, silyl
or alkoxy anions, acetates or sulphonates, and those which are not coordinated, for example
PF6-, BF4-, B(C6H5)4- and other borate derivatives and also various sulphonates, nitrates and
perchlorates.
Apart from purely olefinically coordinated complexes, i.e. complexes in which only olefins
or the counterion are coordinated to the rhodium, mixed complexes in which both the olefin
and further ligands are coordinated to the rhodium are also known. These further ligands can
be, for example, phosphine or phosphite ligands, amines, arsanes or coordinating organic
solvents.
Various mixed complexes of this type have been described in the prior art, e.g. complexes in
which the rhodium is also doubly coordinated by methanol, ethanol, acetone or acetonitrile
as organic solvents in addition to a diene, which is usually COD or NBD, or a phosphine (cf.,
for example, Osborn et al., Angew. Chemie 99 (1987) 1208-1209). Such complexes which
are described in the prior art correspond to a composition represented by one of the general
formulas [Rh(diene)L2]X or [Rh(chiral phosphine ligand)(L)2]X, where diene is 1,5-
cyclooctadiene (COD) or norbomadiene (NBD), L is acetone, acetonitrile, methanol or
ethanol and X is an anion selected from among BF4- and CF3SO3-.


Some of the compounds described in the prior art have been postulated or identified in
solution by means of NMR spectroscopy as intermediates, i.e. in-situ preparations (e.g. in
Schrock et al., J. Am. Chem. Soc. 93 (1971) 2397-2407 for L -methanol or acetone), or as
precursors of catalysts in hydrogenation reactions. Isolation and separate characterization of
these complexes has hitherto not been successful because of their supposedly low stability in
the case of, for example, L = acetone.
Bergbreiter et al. (Tetrahedron Letters (1997), 38 (21), 3703-3706, and Chemical Industries
(Dekker) (1998), 75 (Catalysis of Organic Reactions), 403-414) describe the use of
[Rh(COD)]CF3SO3. However, the structure and the method of preparing the compound
remain undefined and also cannot be deduced from the prior art.
Harry et al. (Inorganica Chimica Acta 97 (1985) 143-150) disclose the preparation and use of
[Rh(COD)]CF3SO3. The structure of the compound described has not been elucidated. The
analytical data obtained do not agree with the structure as proposed above. Isolation of a
complex of the formula [Rh(COD)(L)2]CF3SO3 where L = coordinating solvent as a solid is
not described; the compounds are merely postulated in solution.
In Chem. Ber. 128 (1995) 911-917, Kolle et al. describe the preparation of various olefin-
aquo complexes of rhodium(I). Specifically, the preparation, isolation and use of
[Rh(COD)(H2O)(p-toluenesulphonate)] is disclosed. Furthermore, Kolle et al. describe the
in-situ preparation of a series of complexes of the general formula [Rh(diene)L2]X, where
diene is 1,5-cyclooctadiene (COD) or norbomadiene (NBD), L is acetone or water and X is
an anion selected from among p-CH3(C6H4)SO3- (tosylate, OTs-), CF3SO3- or BF4-. These
compounds are prepared using solid silver salts and in solvent mixtures of water and ethanol
which are not described in more detail. Some of the compounds mentioned have been
postulated as intermediates or, on the basis of NMR-spectroscopic studies, only in solution.
In contrast, experimental confirmation of the bisaquo complexes has not been carried out
successfully. It was only possible to prepare corresponding complexes with monoolefins, e.g.
ethylene, or open-chain 1,3-dienes, e.g. isoprene.
According to Kolle et al., attempts to isolate a complex of the formula [Rh(C0D)(H20)2]X

failed and led, in the case of OTs- as anione X, to the complex [Rh(COD)(H2O)OTs], i.e. a
monoaquo complex. The structure of this complex was able to be confirmed by means of
X-ray structure analysis and the structure determined is shown in the following figure:

It is an object of the present invention to provide new diene-bis-aquo-rhodium(I) complexes.
The object of the invention is achieved by a novel process for preparing diene-bis-aquo-
rhodium(I) complexes which comprises reacting rhodium(I)-olefin compounds with silver
salts in an aqueous solvent mixture, characterized in that the silver salt is not added as a solid
to the reaction mixture but is instead prepared in solution and added in this form.
Furthermore, the invention provides the preparation of diene-bis-aquo-rhodium(I) complexes
of the general formula (I):
[Rh(diene)(H2O)2]X (1)
where diene is a cyclic diene and X is a noncoordinating anion. The present invention also
provides for the use of the diene-bis-aquo-rhodium(I) complexes of the invention in catalytic
reactions.
As cyclic diene in the general formula (1), it is possible to use any cyclic diene which is able
to coordinate to a central metal atom in complexes. According to the invention, cyclic dienes
used can be, for example, cyclic hydrocarbons which have from 5 to 12 carbon atoms and
two C-C double bonds in the ring. According to the invention, preference is given to cyclic
dienes in which the two C-C double bonds are not conjugated. As examples of cyclic dienes
which can be used according to the invention, mention may be made of 1,4-cyclohexadiene,
1,4-cycloheptadiene, 1,5-cyclooctadiene (COD), norbornadiene (NBD) and various

camphene derivatives. Particularly preferred cyclic dienes for the purposes of the invention
are 1,5-cyclooctadiene (COD) and norbornadiene (NBD). Particular preference is given to
1,5-cyclooctadiene (COD).
The radical X in the formula (1) is a noncoordinating anion. According to the invention, X
can be any anion which is known in the technical field as being capable of being present in
noncoordinated form in metaTcomplexes, in particular in rhodium compounds, particularly
preferably in rhodium(I) compounds. As examples of noncoordinating anions which can be
used for the purposes of the present invention, mention may be made of CF3SO3-, BF4-,
B(C6H5)4-, B(C6H3(CF3)2)4-, B(C6F5)4-, PF6-, SbF6- and ClO4-. Particular preference is given
to tetrafluoroborate (BF4-) and trifluoromethylsulphonate (triflate, CF3SO3-).
In a particularly preferred embodiment of the present invention, the diene in the formula (1)
is 1,5-cyclooctadiene (COD) and the anion is BF4-. This complex of the formula
[Rh(COD)(H2O)2]BF4 is named l,5-cyclooctadienebisaquorhodium(I) tetrafluoroborate and
has the structure below:

In a further, particularly preferred embodiment of the present invention, the diene in the
formula (1) is 1,5-cyclooctadiene (COD) and the anion is CF3SO3-. This complex of the
formula [Rh(COD)(H2O)2]CF3SO3 is named l,5-cyclooctadienebisaquorhodium(I)
trifluoromethylsulphonate or triflate and has the structure below:


The novel diene-bis-aquo-rhodium(I) complexes described can be prepared either in solution
or suspension in any solvent, for example halogen-containing solvents, water, alcohols and
ethers, preferably as a solution in water, alcohols such as methanol or ethanol, ethers such as
tetrahydrofuran, dioxane and diethyl ether or acetone or in mixtures thereof, or as isolated *
substances. The diene-bis-aquo-rhodium(I) complexes of the present invention are preferably
prepared as solids.
One method known to those skilled in the art for introducing anionic ligands into metal
complexes is the transmetallation reaction. It is based on the principle that a precursor
compound which is made up of the cation of the desired complex and a replaceable anion is
reacted with a suitable metal salt of the anion to be introduced into the complex. In the past,
silver salts have been found to be particularly useful as metal salts for introducing various
anions into metal complexes, with the appropriate silver salt generally being added as a solid
to the reaction mixture.
The process of the present invention for preparing the diene-bis-aquo-rhodium(I) complexes
of the invention is characterized in that the appropriate silver salt serving as transmetallation
reagent is not added as a solid to the reaction mixture but is instead prepared in solution and
added in this form. To prepare a silver salt solution for use according to the present
invention, preference is given to reacting a silver-containing starting compound, particularly
preferably a basic silver salt such as silver oxide (Ag2O), with a suitable acid in a suitable
solvent so as to eliminate water in the case of Ag2O as starting compound and give a solution
of the desired silver salt. As suitable acid, the acid corresponding to the noncoordinating
anion to be introduced into the diene-bis-aquo-rhodium(I) complex, e.g.
trifluoromethanesulphonic acid for preparing a solution of AgCF3SO3, is chosen.
The preparation of the silver salt solution by reacting Ag2O with the appropriate acid is
preferably carried out in an aqueous medium. An aqueous medium for the purposes of the
invention encompasses water as sole solvent and also all solvent mixtures in which water is
the main component of the mixture and is mixed with one or more water-miscible solvents.
Examples of such water-miscible solvents are alcohols such as methanol, ethanol,
. n-propanol, isopropanol, n-butanol and tert-butanol, ethers such as tetrahydrofuran or


dioxane, and acetone. Furthermore, an aqueous medium for use according to the invention
can comprise water and a water-miscible solvent together with at least one further solvent
which is not miscible with water, as long as the solvent mixture forms a homogeneous phase.
Examples of such water-immiscible solvents which can be used according to the invention
are diethyl ether and methyl tert-butyl ether. The use of water as solvent for preparing the
silver salt solution according to the invention is particularly preferred.
The respective acid is preferably used in an excess over the silver oxide for preparing the
silver salt solution. This excess of acid can be up to 0.5 molar equivalents and is preferably
in the range from 0.01 to 0.15 molar equivalents. The particularly preferred excess of acid
over the silver oxide in an individual case can depend on the type of acid used; in particular,
the silver oxide should have dissolved completely after the addition is complete. To prepare
an AgBF4 solution by the method according to the invention, the acid HBF4 is particularly
preferably used in an excess of about 0.03 molar equivalents over the silver oxide, while for
the preparation of an AgCF3SO3 solution according to the invention the particularly preferred
excess of CF3SO3H is about 0.07 molar equivalents.
Rhodium(I)-olefm compounds which can be used as starting materials in the process of the
present invention are in principle all rhodium(I)-olefin compounds which can react with the
silver salt solution according to the invention in a transmetallation reaction to form the
diene-bis-aquo-rhodium(I) complexes of the invention. As preferred rhodium(I)-olefin
compounds for the purposes of the present invention, it is possible to use complexes of the
general formula [Rh(diene)Y]2 in which Y is Cl, Br or I and diene is as defined above. A
particularly preferred rhodium(I)-olefin compound which can serve as starting compound for
the transmetallation reaction is the dimeric rhodium complex [Rh(COD)Cl]2-
As aqueous solvent mixture in which the reaction of the rhodium(I)-olefin compound with
the silver salt can be carried out by the process of the invention, it is possible to use all
solvent mixtures in which water is present as a constituent. As further constituents of a
solvent mixture which can be used according to the invention it is possible to use all water-
miscible solvents. The aqueous solvent mixture preferably comprises water together with up
to 10% by volume of at least one alcoholic solvent. As preferred alcoholic solvents, it is


possible according to the invention to use, in particular, methanol, ethanol, n-propanol,
isopropanol, n-butanol and tert-butanol.
In the process of the invention, the reaction of the rhodium(I)-olefin compound with the
appropriate silver salt in the aqueous solvent mixture is preferably carried out by adding the
previously prepared silver salt solution to a solution or suspension of the rhodium(I)-olefin
compound in an aqueous solvent mixture according to the invention. In the addition of the
silver salt solution to the solution or suspension of the rhodium(I)-olefin compound in the
aqueous solvent mixture, the total amount of silver salt solution can be added all at once or
the silver salt solution can be added dropwise over a relatively long period of time, for
example up to one hour.
After all of the silver salt solution has been added, the reaction mixture is stirred for a
suitable period of time, resulting in a silver salt formed as by-product of the transmetallation
reaction being precipitated as a solid. To isolate the desired diene-bis-aquo-rhodium(I)
complex, the precipitated solid is subsequently filtered off and washed as often as necessary
with a suitable solvent, preferably water. The solvent can be removed from the resulting
filtrate in a manner known in the technical field, for example by evaporation on a rotary
evaporator, in order to isolate the desired diene-bis-aquo-rhodium(I) complex as a solid.
Both in the preparation of the silver salt solution and in the reaction with the rhodium(I)-
olefin compound, the working temperature should, according to the present invention, be
selected so that the resulting diene-bis-aquo-rhodium(I) complexes of the present invention
do not decompose. For this reason, a temperature of 40°C should preferably not be exceeded
as working temperature as long as the diene-bis-aquo-rhodium(I) complexes of the invention
are present in solution. The reactions are particularly preferably carried out at room
temperature.
The diene-bis-aquo-rhodium(I) complexes of the invention can be used in catalytic reactions,
i.e. both in homogeneous catalysis and in heterogeneous catalysis. The diene-bis-aquo-
rhodium(I) complexes of the present invention are particularly suitable for use in asymmetric
and symmetric catalytic hydrogenations of double bonds, for example C-C, C-O, C-N or N-N


double bonds. Another field of application comprises catalytic hydroformylation reactions
and hydrosilylations.
Furthermore, the diene-bis-aquo-rhodium(I) complexes of the invention can be used as
precursors for other catalytically active species. The diene-bis-aquo-rhodium(I) complexes of
the invention can be used for preparing chirally nonselective, diastereoselective or
enantioselective catalytically active species. To generate such catalytically active species, the
diene-bis-aquo-rhodium(I) complexes of the invention can be reacted with various achiral
and chiral ligands, for example triphenylphosphine, ferrocenylphosphines, alkylphosphines
or chiral phosphine ligands, with ligand exchange.
The diene-bis-aquo-rhodium(I) complexes of the invention can also be used for preparing
heterogeneous catalysts by any of the processes known in the technical field for
immobilizing soluble organic metal complexes. In a particularly preferred embodiment, a
diene-bis-aquo-rhodium(I) complex according to the invention can be used as supported or
immobilized noble metal catalyst.
Examples
Example 1: Preparation of [Rh(COD)(H2O)2]BF4
4.63 g of aqueous HBF4 solution (about 50% strength, 26.36 mmol of HBF4, excess over
Ag2O: 0.03 molar equivalent) and 10 g of distilled water are weighed into a glass beaker. In
addition, 2.96 g of Ag2O (12.77 mmol) are weighed out onto a paper boat. The Ag2O is
carefully added from the paper boat to the aqueous HBF4 solution over a period of one
minute, whereupon the mixture is stirred vigorously. An AgBF4 solution is obtained.
6.0 g of [Rh(COD)Cl]2 (41% of Rh, 2.46 g of Rh, 23.9 mmol) are weighed into a second
glass beaker and suspended in 10 g of distilled water and 0.3 g of ethanol (corresponding to
about 1.5% by volume of the resulting total solution) by stirring (RCT Basic, setting 4-5) for
seven minutes. The entire AgBF4 solution prepared in the first step is poured into the

resulting suspension while stirring, resulting in a precipitate being formed. The light-yellow
suspension obtained is stirred for about 30 minutes. The precipitate is subsequently filtered
off and washed twice with about 5 ml of distilled water. The solution obtained is finally
evaporated at 40°C under reduced pressure on a rotary evaporator. 7.96 g of the title product
are isolated (30.3% of Rh, 2.41 g of Rh, 23.4 mmol, yield: 98% based on Rh).
Analysis: C8H16O2BF4Rh, M = 333.9233 g/mol.
1H-NMR (CDC13, 500 MHz): δ (ppm) = 1.57 (s, 4 H), 5.46-5.57 (m, 8 H).
1H-NMR (d-dioxane, 500 MHz): δ (ppm) = 1.73 (dt, J = 7.2 Hz, J = 8.5 Hz, 4 H), 2.50-2.53
(m, 4 H), 4.05 (m, 4 H).
1H-NMR (MeOD, 500 MHz): δ (ppm) = 1.72 (dt, J = 6.9 Hz, J « 8.5 Hz, 4 H), 2.51-2.54 (m,
4 H), 4.07 (m, 4 H).
IR (KBr, cm-1): 3436 (vs), 2939 (m), 2876 (m), 2803 (m), 1639 (m), 1467 (w), 1429 (m),
1325 (w), 1299 (m), 1061 (vs), 958 (m), 794 (m), 521 (m).
% of Rh (measured by ICP = inductively coupled plasma): % theoretical: 30.82
% actual: 30.30
Elemental analysis:
% of C, theoretical 28.77
% of C actual 28.56
% of H, theoretical 4.83
% of H actual 4.98
The structure of the complex was confirmed by X-ray crystal structure analysis.
Example 2: Preparation of [Rh(COD)(H2O)2[CF3SO3


4.92 g of Ag2O (21.26 mmol) and 10 g of distilled water are weighed into a glass beaker and
carefully admixed with 4.1 ml of trifluoromethanesulphonic acid (about 98% pure,
45.40 mmol, excess over Ag2O: 0.07 molar equivalents). A further 10 g of distilled water are
added while stirring vigorously. An AgCF3SO3 solution is obtained.
9.94 g of [Rh(COD)Cl]2 (41% of Rh, 4.08 g of Rh, 39.6 mmol) are weighed into a second
glass beaker and suspended in 10 g of distilled water and 0.82 ml of ethanol (corresponding
to about 0.5% by volume of the resulting total solution) and 12.7 ml of methanol
(corresponding to about 9.5% by volume of the resulting total solution) by stirring (RCT
Basic, setting 4-5) for seven minutes. The entire AgCF3SO3 solution prepared in the first step
is poured into the resulting suspension over a period of 30 minutes while stirring, and the
AgCF3SO3 solution is rinsed twice with 5 g each time of distilled water. A precipitate is
formed. The light-yellow suspension obtained is stirred for about 30 minutes. The precipitate
is subsequently filtered off and washed six times with about 5 ml of distilled water. The
solution obtained is finally evaporated at 40°C under reduced pressure on a rotary
evaporator. 15.3 g of the title product are isolated as an orange solid (25.3% of Rh, 3.87 g of
Rh, 37.60 mmol, yield: 95% based on Rh).
Analysis: C9H16O5SF3Rh, M = 396.1879 g/mol.
1H-NMR (CDCl3, 500 MHz): δ (ppm) = 1.25 (s, 4 H), 2.50-2.53 (m, 4 H), 4.09 (m, 4 H).
1H-NMR (d-dioxane, 500 MHz): δ (ppm) = 1.66 (dt, J = 7.2 Hz, J = 8.5 Hz, 4 H), 2.45-2.47
(m, 4 H), 4.02 (m, 4 H).
'H-NMR (MeOD, 500 MHz): 8 (ppm) = 1.63 (dt, J = 6.9 Hz, J = 8.5 Hz, 4 H), 2.38-2.40 (m,
4 H), 3.93 (m, 4 H).
13C-NMR (MeOD, 125 MHz): δ (ppm) = 31.57 (d, 4 C), 78.81 (d, J = 15,2 Hz, 4 C), 121,61
(q, J = 318.5 Hz).
IR (KBr, cm-1): 3415 (vs), 2998 (s), 2924 (s), 2879 (s), 1646 (m), 1433 (w), 1254 (vs), 1178

(vs), 1032 (vs), 969 (m), 643 (s), 582 (m), 518 (m).
% of Rh (measured by ICP = inductively coupled plasma): % theoretical: 25.97
% actual: 25.30
Elemental analysis:
% of C, theoretical 27.28
% of C actual 26.95
% of H, theoretical 4.07
% of H actual 4.3
% of S theoretical 8.09
% of S actual 8.33
The structure of the complex was confirmed by X-ray crystal structure analysis.

We Claim:
1. Diene-bis-aquo-rhodium(I) complex of the formula:
[Rh(diene)(H2O)2]X (I)
where diene is a cyclic diene and X is a noncoordinating anion.
2. The diene-bis-aquo-rhodium(I) complex as claimed in claim 1,
wherein diene is 1,5-cyclooctadiene (COD) or norbornadiene
(NBD).
3. The diene-bis-aquo-rhodium(I) complex as claimed in claim 1,
wherein X is a noncoordinating anion selected from the group
consisting of BF4- and CF3SO3-
4. The diene-bis-aquo-rhodium(I) complex as claimed in claim 2,
wherein x is a noncoordinating anion selected from the group
consisting of BF4- and CF3SO3-
5. The diene-bis-aquo-rhodium(I) complex as claimed in claim 1
having the name 1,5-cyclooctadienebisaquorhodium (I)
tetrafluoroborate.

6. The diene-bis-aquo-rhodium(I) complex as claimed in claim 2
having the name 1,5-cyclooctadienebisaquorhodium (I)
tetrafluoroborate.
7. Diene-bis-aquo-rhodium(I) complex as claimed in claim 1 having
the name 1,5-cyclooctadienebisaquorhodium (I)
tri fluoromethylsulphonate.
8. Diene-bis-aquo-rhodium(I) complex as claimed in claim 2 having
the name 1,5-cyclooctadienebisaquorhodium (I)
trifluoromethylsulphonate.
9. The diene-bis-aquo-rhodium(I) complex as claimed in claim 1,
wherein the complex is in the form of a solid.
10. Process for preparing a diene-bis-aquo-rhodium(I) complex as
claimed in claim 1, which comprises reacting a rhodium(I)-olefin
compound with a silver salt in an aqueous solvent mixture as a
reaction mixture, wherein the silver salt is prepared in solution and
is added to the reaction mixture.
11. The process for preparing a diene-bis-aquo-rhodium (I) complex as

claimed in claim 10, wherein the silver salt is prepared in solution
by reacting silver oxide (Ag2O) with the acid corresponding to the
noncoordinating anion of the diene-bis-aquo-rhodium(I) complex.
12. The process for preparing a diene-bis-aquo-rhodium (I) complex as
claimed in claim 10, wherein the acid is used in an excess of up to
0.5 molar equivalents over the silver oxide.
13. The process for preparing a diene-bis-aquo-rhodium (I) complex as
claimed in claim 10, wherein the preparation of the silver salt is
carried out in an aqueous medium.
14. The process for preparing a diene-bis-aquo-rhodium (I) complex as
claimed in claim 11, wherein the preparation of the silver salt is
carried out in an aqueous medium.
15. The process for preparing a diene-bis-aquo-rhodium (I) complex as
claimed in claim 10, wherein the rhodium(I)-olefin compound is
[Rh(COD)Cl]2.
16. The process for preparing a diene-bis-aquo-rhodium (I) complex as
claimed in claim 10, wherein the aqueous solvent mixture
comprises water together with up to 10% by volume of at least one
alcoholic solvent.

17. The process for preparing a diene-bis-aquo-rhodium (I) complex as
claimed in claim 11, wherein the aqueous solvent mixture
comprises water together with up to 10% by volume of at least one
alcoholic solvent.
18. The process for preparing a diene-bis-aquo-rhodium (I) complex as
claimed in claim 16, wherein the alcoholic solvent is selected from
methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-
butanol.
19. In a catalytic reaction, the improvement comprising carrying out
said reaction in the presence of diene-bis-aquo-rhodium(I)
complex as claimed in claim 1.
20. A method for preparing a heterogeneous catalyst, comprising
carrying out said method in the presence of a diene-bis-aquo-
rhodium(I) complex as claimed in claim 1.
21. A method for preparing a chirally nonselective, diastereoselective
or enantioselective catalytically active species comprising carrying
out said method in the presence of a diene-bis-aquo-rhodium(I)
complex as claimed in claim 1.

22. The method as claimed in claim 21, wherein the diene-bis-aquo-
rhodium(I) complex is reacted with achiral and/or chiral ligands
with ligand exchange.
23. The method as claimed in claim 22, wherein the achiral and/or
chiral ligands are selected from the group consisting of
triphenylphosphine, ferrocenyiphosphine, alkylphosphine and
chiral phosphine.


Diene-bis-aquo-rhodium(I) complex of the formula:
[Rh(diene)(H2O)2]X (I)
where diene is a cyclic diene and X is a noncoordinating anion.

Documents:

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447-kolnp-2006-granted-abstract.pdf

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Patent Number 247153
Indian Patent Application Number 447/KOLNP/2006
PG Journal Number 13/2011
Publication Date 01-Apr-2011
Grant Date 29-Mar-2011
Date of Filing 27-Feb-2006
Name of Patentee UMICORE AG & CO.KG
Applicant Address RODENBACHER CHAUSSEE 4 63457 HANAU GERMANY
Inventors:
# Inventor's Name Inventor's Address
1 RIVAS-NASS ANDREAS AM HUNDACKER 10 55257 BUDENHEIM GERMANY
2 WIDMER, JURGEN HEIDELBERGE STRASSE 27A 64285 DARMSTADT GERMANY
3 BRIEL, OLIVER TULPENHOFSTTRASSE 25 63067 OFFENBACH GERMANY
4 KARCH, RALF KATHE-KOLLWITZ-STRASSE 24 63801 KELINOSTHEIM GERMANY
5 PETER, GERHARD JAHNSTRASSE 11, 63579 FREIGERICHT GERMANY
PCT International Classification Number B01J 31/22
PCT International Application Number PCT/EP2004/008964
PCT International Filing date 2004-08-10
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 103 39 790.6 2003-08-28 Germany