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CHIRALITY 12:411420 (2000)

Immobilization of Rhodium Complexes in Chiral

OrganicInorganic Hybrid Materials
Laboratoire de Chimie Organometallique, Ecole Nationale Superieure de Chimie de Montpellier,
Montpellier, France

ABSTRACT Two new alkoxysilylated derivatives of ()-(1R,2R)-1,2-diaminocyclo-

hexane: M = N-[(triethoxysilyl)propyl]-()-(1R,2R)-1,2-diaminocyclohexane and B =
N,N-bis[(triethoxysilyl)propyl]-()-(1R,2R)-1,2-diaminocyclohexane have been synthe-
sized. Their complexation with [Rh(cod)Cl]2 in the presence of TEOS = Si(OEt)4, fol-
lowed by sol-gel hydrolysis-condensation, afforded new catalytic chiral hybrid materials.
Evidence for the presence of the organic moieties complexed by rhodium in these solids
was obtained by UV-visible spectroscopy, FT-IR studies, solid state 13C and 29Si CP-MAS
NMR analysis, energy-dispersive X-ray (EDX) techniques, and elemental analysis. The
nitrogen sorption studies and BET analyses ranged these solid gels from nonporous to
highly porous materials. The catalytic activities and selectivities of the solid materials
have been studied in the asymmetric hydrogen-transfer reduction of prochiral ketones
and compared to that of the homogeneous rhodium complexes of the ligands M and B.
The hybrid materials appeared interesting supports for enantioselective heterogeneous
catalysis leading to chiral alcohols with ee up to 58% in the reduction of acetophenone
and up to 98% in the case of the more hindered related ketones. The catalytic properties
as a function of the nature of chiral hybrid solid are discussed. Chirality 12:411420,
2000. 2000 Wiley-Liss, Inc.

KEY WORDS: hybrid materials; chiral polymeric networks; sol-gel process; heteroge-
neous catalysts ()-(1R,2R)-1,2-diaminocyclohexane; enantioselective
catalysts; hydrogen-transfer reduction

One of the most important areas of synthetic organic opens the possibility to heterogenize transition metal cata-
chemistry consists in developing new methodologies for lytic species. However, problems related to the stability
efficient asymmetric syntheses. Many organic molecules and selectivity of the catalyst sometimes remain and sup-
can now be synthesized with near-complete enantioselec- ported homogeneous catalysts do not always compare fa-
tivity.16 Bidentate auxiliaries with C2 symmetry have at- vorably with the soluble catalytic species.19 The develop-
tracted much attention and proved to be highly efficient, ment and the design of enantioselective heterogenous cata-
leading to high asymmetric induction in chemical transfor- lysts is still a challenging area.27,28
mations.7 Transition metal complexes containing chelating In the last decade the sol-gel process, which emerged as
ligands with C2 symmetry also constitute the most inter- a very interesting way to prepare inorganic materials29 was
esting class of chiral catalysts to achieve homogeneous successfully used to prepare heterogeneous catalysts.30,31
asymmetric reactions.4 Complexes of transition metals
Moreover, owing to the mild reaction conditions used, the
containing Noyoris BINAP ligand,811 for example, allow
sol-gel chemistry allows easy preparation of hybrid solid
the asymmetric hydrogenation reaction of unsaturated sub-
materials.32,33 Hybrid silica-based materials, which can be
strates or the asymmetric isomerization of allylic amines
with extremely high enantioselectivities. Even simple and simply defined as a solid associating an organic component
readily available molecules such as trans-1,2-diamino- and a silica fragment, are receiving much attention owing
cyclohexane derivatives were shown to be of great interest to their well-defined structure and their stability.3442 The
as chiral reagents, as scaffolds, or as ligands for catalysis.12 hydrolysis-condensation reaction of organic molecules
Most of the above reactions were performed in homoge- functionalized by Si(OR)3 groups leads to a wide variety of
neous media. The problems associated with the recovery
of homogeneous catalysts and their separation from the
Dedicated to Professor Ryoji Noyori in recognition of his outstanding in-
reaction products1318 and the difficulties associated with novative contributions.
the recycling of the catalytic species have in part been *Correspondence to: Joel J.E. Moreau, Laboratoire de Chimie Organo-
addressed by immobilization on a heterogeneous solid sup- metallique, UMR CNRS 5076, Ecole Nationale Superieure de Chimie de
Montpellier, 8 rue de lEcole Normale, 34296 Montpellier Cedex 05,
port such as polymers or silicas.1926 The grafting of chiral France. E-mail:
ligands on the surface of organic or inorganic polymers Received for publication 29 November 1999; Accepted 13 January 2000
2000 Wiley-Liss, Inc.

Scheme 1. Sol-gel hydrolysis of poly(trialkoxy)organosilanes.

Scheme 2. Synthesis of molecular precursors M and B.

hybrid polysilsesquioxane gels. The presence of nonhydro- able mixture of cis and trans-diaminocyclohexane (30/70)
lysable Si-C bonds35,36 led to a 3D network which can be according to the literature.52,53
described as siloxane chains cross-linked by bridging or- The preparations of the monosilylated M and the bis-
ganic substructures (Scheme 1). This approach offers silylated derivatives B, were achieved stepwise to avoid the
great potential for material design in many applications. formation of a mixture of both M and B, which were found
Highly porous materials with high surface areas have been difficult to separate. A mixture containing a 2:1 molar ratio
obtained in some cases, attributed to the rigid property of of ()-(1R,2R)-1,2-diaminocyclohexane and (3-chloro-
the cross-linking organic moieties.35,36 A control of the propyl)triethoxysilane was heated to 87C in a sealed tube
pore structure has also been reported by the use of a mo- for 18 h. The extraction with pentane followed by filtration
lecular template.4145 and then distillation at reduced pressure afforded M as a
The sol-gel processing of organofunctional metal alkox- colorless liquid in 70% yield. B was obtained in a 60% yield
ides has also been used to prepare hybrids containing tran- as a crude viscous liquid, following a similar procedure
sition metal. The incorporation of Lewis bases or ligands with a 2:1 molar mixture of M and (3-chloropropyl)trieth-
has led to materials with complexing or catalytic proper- oxysilane at 110C for 18 h.
ties.46,47 Heterogeneous metal catalysts and immobilized
molecular catalytic species with high stability have been Synthesis and Characterization of the Chiral
reported using a sol-gel approach.46,47 Very recently, new Hybrid Materials
hybrid silica gels with bidentate malonamide units have The hydrolysis-condensation of the precursors M and B
been shown to be highly efficient extracting solids for ac- were performed with or without added tetraethoxysilane
tinides.48 The approach involving hybrid organic-inorganic (TEOS) under mild reaction conditions in ethanol by add-
materials is quite interesting since the properties of the ing a stoichiometric amount of water. For characterization
material can be tailored on a molecular basis according to studies and for comparison we first prepared hybrid gels
the structure and properties of the precursors (Scheme 1). (without incorporating rhodium) from M and B. No gel
Our current interest in the use of hybrid silicas as sup- formation occurred upon hydrolysis of pure M. It was ob-
port for heterogeneous catalysts49,50 has led us to investi- tained upon co-hydrolysis condensation with added TEOS.
gate the incorporation of chiral organic molecules in the The hydrolysis of pure B containing two silyl substituents
mixed 3D network of hybrids. We were particularly inter- rapidly gave a gel. In all cases gelation occurred within 3 h
ested in incorporating molecules with C2 symmetry, to pro- without the use of any added catalyst. Nucleophilic activa-
duce a chiral polymeric hybrid network, and in immobiliz- tion by the nitrogen atoms present in M and B accounts for
ing transition metal complexes on these chiral supports. the fast hydrolysis-condensation process.54,55 After the for-
We report here the preparation of hybrid solids containing mation of the gels, these were aged for 1 week, then pow-
(1R,2R)-diaminocyclohexane units and their use to immo- dered, washed, and dried under vacuum and analyzed.
bilize rhodium catalysts. We explored the preparation of The synthesis of the gel from monosilylated compound
various gels containing rhodium chiral diamine complexes. M was achieved in the presence of 5 mol equivalent of
The catalyst selectivity has been studied as a function of TEOS (Scheme 3). The gel, M-5, (M stands for monosi-
the structure and stoichiometry of the hybrid using mono- lylated derivative and 5 for the number of moles of TEOS)
silylated or bis-silylated chiral diamine precursors. Part of was obtained quantitatively.
this work has been previously published.51 The synthesis of the gels from the bis-silylated com-
pound B was obtained without addition of TEOS owing to
RESULTS AND DISCUSSION the two functional trialkoxysilyl groups which allow an
Synthesis of the Functionalized Diamines M and B easy cross-linking of the silicate framework.35,36 Addition
of 2 mol equivalent of H2O to a solution of B in EtOH
The synthesis of monosilylated M and bis-silylated B rapidly led to gel B-0 (B stands for bis-silylated and 0 for
amines (Scheme 2) was performed with ()-(1R,2R)- the absence of TEOS) (Scheme 4).
diaminocyclohexane after resolution of commercially avail- The solid stoichiometry was determined upon elemental

Scheme 3. Synthesis of monosilylated gel M-5.

analysis of the obtained material. It differs somewhat from

the silsesquioxane stoichiometry shown in Schemes 3 and
4, used there for simplicity. It indicates that the material
contained remaining uncondensed OH and OEt groups at
silicon. The results are quite similar to those of previous
observations with related materials.36,37
The hybrid gel containing the chiral diaminocyclohex-
ane units were characterized by IR and solid state 13C and
Si NMR. The measurements were performed using the
CP-MAS technique in order to enhance signal intensity.56 Scheme 4. Synthesis of bis-silylated gel B-0.
The 13C solid state NMR are consistent with the presence
of the organic unit in the hybrid network (cf. Fig. 1). The
gel M-5 exhibits two very broad signals at 5075 and 2050
ppm. The first one corresponds to the carbon atoms linked
to nitrogen and to residual uncondensed ethoxy groups
(O-CH2). The second one corresponds to the cyclic and
also inner carbon atom of the n-propyl group (C-CH2-C).
Two signals centered at 18 and 8 ppm are also present in
the spectrum corresponding, respectively, to the methyl
carbon of residual ethoxy group and to the carbon atom
bonded to silicon. The spectrum of gel B-0 is similar, with
two broad signals at 2040 ppm and 5068 ppm, a sharp
signal at 18 ppm (residual ethoxy group), and a weak signal
at 8 ppm.
The 29Si solid state NMR allowed the characterization of
the silicate substructures in the hybrid network. Again, the
CP-MAS technique was used so as to recover higher signal
intensity for these materials. The gel M-5 presented a
spectrum with essentially two groups of signals (Fig. 2).
The first is a broad signal centered at -66 ppm correspond-
ing to T units (trifunctional silicate: C-SiO3) and the second
at -103 and -110 ppm represents the different Q units
(quadrifunctional silicate: SiO4). The gel prepared without FIG. 1. C CP-MAS solid state NMR of B-5.
TEOS, B-0, exhibits only a large peak from 50 to 75 ppm
(Fig. 2). It represents overlapping signals corresponding to
T units (C-SiO3). The absence of signal in the region 100,
110 ppm demonstrates that no cleavage of the Si-C bonds
had occurred during gel formation.
The surface properties of gels M-5 and B-0 were stud-
ied by nitrogen sorption experiments according to BET.57
Surface areas of 280 m2 g1 and 20 m2 g1 were respectively
determined for materials M-5 and B-0.

Rhodium Complexes Containing Chiral

Hybrid Materials
We then studied the incorporation of rhodium species in
the hybrid network. The approach was first to form a rho-
dium complex with the diamine precursor and then to per-
form hydrolysis to prepare the hybrid gel. In this way the FIG. 2. 29
Si CP-MAS solid state NMR of M-5 and B-0.

Scheme 5. Synthesis of rhodium-complexed monosilylated gels with TEOS.

solid material is built around the metal species. It differs the solid material appeared similar to the species in solu-
from the classical grafting of a metallic species at the sur- tion.
face of a solid material and may give the complex a higher The rhodium-containing hybrids were also studied by
stability. It may result in enhanced stability of the catalytic solid-state NMR. The CP-MAS 13C NMR spectra of gels
materials. MRh-2 and MRh-5 are similar to that of the correspond-
ing noncomplexed gel M-5, apart from a broad signal rang-
Synthesis of gels from monosilylated precursor M. ing from 7090 ppm. This broad signal corresponds to the
The precursor M was first reacted with 0.5 mol equiva- sp2 carbon of cyclooctadiene (cod) ligand initially com-
lent of [Rh(cod)Cl]2 in ethanol. Evidence for the complex- plexed with [Rh(cod)Cl]2. It appears that the cod ligand is
ation of the diamine ligand M with [Rh(cod)Cl]2 in ethanol retained in the coordination sphere of the rhodium atom in
as solvent was obtained by UV-visible analysis. The rho- the solid material. The 29Si CP-MAS NMR spectra of
dium dimer [Rh(cod)Cl]2 complex exhibits an absorption MRh-2 and MRh-5 are similar to that of the rhodium free
at 350 nm. Upon reaction with M, a new absorption maxima hybrid M-5.
appears at 383 nm. The intermediate complex of M was The BET surface areas of the two materials were deter-
then subjected to hydrolysis and condensation in the pres- mined and the results are shown in Table 1. A low surface
ence of added TEOS (Scheme 5). area was found for MRh-2, whereas a much higher value
In order to study the dilution effect of the diamine- was determined in the case of MRh-5. The latter is similar
rhodium complex with TEOS, two gels were prepared from to that of the rhodium-free hybrid M-5.
M with a 2:1 and a 5:1 molar ratio of TEOS: M respectively For comparison, another catalytic material, MRh-GS,
called gels MRh-2 and MRh-5, (Rh stands for rhodium- (GS means grafted silica) was prepared using a conven-
complexed material). tional immobilization technique. After activation of a com-
The compositions of all these materials were analyzed by mercial high surface area silica58,59 the ligand M was
atomic percent determination using EDX techniques and grafted following the literature method.60 The immobilized
also by elemental analysis. The results are summarized in ligand was then complexed with [Rh(cod)Cl]2 to give
Table 1, and shows a quantitative incorporation of rhodium MRh-GS (Scheme 6).
into the hybrid material. Solid UV-visible analyses per-
formed on the gels also showed the presence of an absorp- Synthesis of gels from bis-silylated precursor B. The
tion maximum at 383 nm. The rhodium diamine complex in rhodium-containing hybrids were prepared from B in a
way similar to that used in the case of M. The bis-silylated
precursor B was first treated with [Rh(cod)Cl]2 in EtOH to
TABLE 1. EDX, elementary, and surface area analysis of give a species which exhibits a UV-visible absorption
rhodium-complexed gels maxima at 383 nm. It was then hydrolyzed with or without
added TEOS (Scheme 7).
EDX Elem.
Theoretical analysis Anal. Surface area
Gel Rh/Si Rh/Si Rh/Si m2 g1
MRh-2 0.33 0.33 0.32 3
MRh-5 0.16 0.16 0.16 224
MRh-GS 0.09 0.09 (a) (a)
BRh-0 0.5 0.49 0.49 5
B1/2Rh-0 0.25 0.25 0.25 (a)
BRh-1 0.33 (a) 0.33 3
BRh-0 0.2 0.19 (a) 11

(a) Not determined. Scheme 6. Preparation of grafted rhodium-complexed gel, MRh-GS.


Scheme 7. Synthesis of rhodium-complexed bis-silylated gels.

Four complexed gels were synthesized according to two Catalytic Properties of the Chiral Hybrids
criteria. Gels BRh-0 and B1/2Rh-0 were prepared with-
out added TEOS, respectively using 1 and 0.5 mol equiva- Chiral diamine transition metal complexes have been
lent [Rh(cod)Cl]2 vs. B in order to study the effect of the used as catalysts for the enantioselective reduction of ke-
amount of the Rh entity in the material. On the other hand, tones.6169 We evaluated our hybrid materials, containing
gels BRh-1 and BRh-3 were synthesized with an identical rhodium chiral diaminocyclohexane complexes, as cata-
1:1 ratio of [Rh(cod)Cl]2 vs. B in the presence of varying lysts in the heterogeneous catalytic transfer hydrogenation
TEOS, 1 mole or 3 moles of TEOS, respectively, in order to reaction.
examine the dilution effect in silica. We first tested the catalytic activities and selectivities of
The solid materials were isolated quantitatively. The ana- the rhodium-complexed molecular precursors, M:Rh and
lytical results (Table 1), as indicated by the Rh to Si ratios, B:Rh, in solution for the hydrogen-transfer reduction of
are consistent with a complete incorporation of Rh in the acetophenone (Scheme 8). The corresponding solid mate-
collected solid material. The UV-visible spectra of BRh-0, rials with various compositions according to their prepara-
B1/2Rh-0, BRh-1, and BRh-3 also showed absorption tion procedure were then tested as enantioselective cata-
maxima at 383 nm similar to the species in solution. The lysts.
solid state NMR analysis showed characteristics similar to The results obtained for the catalysts derived from the
those observed with B-0 and the previous rhodium- monosilylated precursors catalysts are given in Table 2.
containing materials MRh-2 and MRh-5. A broad signal at The solid catalysts MRh-2 and MRh-5 (entries 2, 3) lead
7090 ppm was found in the 13C CP-MAS NMR spectrum of to ee 2225%, significantly higher than that found in the
the gels. This result indicates that the cyclooctadiene moi- case of the homogeneous catalyst M:Rh (entry 1, ee =
ety still remains in the coordination sphere of rhodium in 14%). The stoichiometry of the solid support, which varied
the solid materials. As expected, the 29Si CP-MAS NMR according to the proportion of TEOS added in the prepa-
spectra of BRh-0 and B1/2Rh-0 were not significantly ration of the catalyst (entries 2 and 3), shows no significant
different from the spectrum of B-0. The spectra of BRh-1
and BRh-3 showed additional resonances in the -100 to TABLE 2. Hydrogen-transfer reduction of acetophenone at
-110 ppm region characteristic of the presence of Q (SiO4) room temperature with rhodium complexed M and B and
substructures (resulting from the hydrolysis condensation their corresponding gels
of TEOS) in the hybrid network of these gels. All the hy-
brid gels prepared from bis-silylated precursor B showed Reaction time Conversion
low BET surface areas ranging from 3 to 11 m2 g1 (cf. Entry Catalyst (d) (%) ee (%)
Table 1). 1 M:Rh 5 95 14
2 MRh-2 7 70 22
3 MRh-5 5 80 25
4 MRh-GS 14 10 22
5 B:Rh 5 95 26
6 BRh-0 5 75 58
7 B1/2Rh-0 8 60 54
8 BRh-1 7 60 10
Scheme 8. Hydrogen-transfer reduction of acetophenone with rho- 9 BRh-3 8 20 15
dium-complexed M and B and hybrid gels.

effect on the enantioselectivity of the reaction since similar TABLE 3. Hydrogen-transfer reduction of prochiral
ees were obtained. ketones with hybrid gel BRh-0 at room temperature
It is interesting to note that the catalyst prepared by
using the conventional grafting of the catalytic species at time Conver- ee Config-
the surface of silica gave a similar enantioselectivity (entry Entry R1 R2 (d) sion (%) uration
4). However, larger differences appeared in the catalyst
1 CH3 Ph 5 75 58 S
activity. The highest conversion is obtained for the catalyst
2 C8H17 Ph 7 80 40 S
in solution and the lowest for the grafted species. Interest- 3* CBu Ph 2 100 63 R
ingly the hybrid catalyst showed an efficiency much higher 4 Me o-MePh 7 41 78 S
than the grafted one, although lower than the rhodium 5 Me o-OMePh 7 30 80 S
complex in solution. The higher conversion observed (en- 6 Me m-OMePh 7 72 22 S
tries 2, 3) may be related to a higher stability of the hybrid 7 Me p-OMePh 7 34 39 S
catalyst compared to the rhodium complex immobilized at 8 Me 1Np 7 28 87 S
9 Me 2Np 7 30 98 S
the surface of silica. The catalytic material MRh-5 (entry
3) with higher porosity and surface area than MRh-2 (en- *The reaction was performed at 60C.
try 2) gave a higher conversion. The results obtained with
the catalysts derived from the bis-silylated derivatives are
also presented in Table 2.
The major result to be pointed out here is that a better We synthesized hybrid organic-inorganic materials con-
selectivity is found when the gels are prepared without taining chiral units using the sol-gel hydrolysis condensa-
added TEOS (entries 6, 7). The ee obtained in homoge- tion of silylated chiral ()-(1R;2R)-trans-1,2-diamino-
neous conditions (entry 5) is lower than those found with cyclohexane derivatives. The resulting chiral solids are of
the former materials (almost doubled ee). Similar enanti- interest for the preparation of enantioselective heteroge-
oselectivities were obtained (54 and 58%) when the amount neous catalysts. Higher selectivities were obtained from
of rhodium varied in the materials (entries 6, 7). The en- the rhodium-complexed hybrid gels for the hydrogen-
transfer reduction of acetophenone compared to those per-
antioselectivity results are better than those found for ma-
formed in homogeneous media. The gels prepared from
terials prepared from the monosilylated derivative. Entries
pure bis-silylated ligand rhodium complex gave the highest
8 and 9 show the results obtained with materials prepared
enantioselectivities. An influence of the secondary struc-
with TEOS. When compared with entry 6, for which the ture of the chiral 3D network may account for that en-
material was prepared without TEOS, a marked decrease hanced selectivity. The latter dramatically decreased when
in selectivity occurred. This result may be indicative of the the catalysts were prepared with added TEOS. In this case,
role played by the hybrid silica matrix. When no TEOS was the chiral diaminocyclohexane units are separated owing
used, the network consists of only chiral diaminocyclohex- to the dilution effect in TEOS.
ane units linked by siloxane bridges. The secondary struc-
ture of the chiral 3D network may have some influence on EXPERIMENTAL SECTION
selectivity. When TEOS is added to the preparation, the
All manipulations were performed under inert gas atmo-
diaminocyclohexane units are separated from each other
sphere (N2 or Ar) using a vacuum line and Schlenk tech-
and the selectivities are closer to the other values. The
niques. All solvents were dried and distilled before use
effect of the structure of the hybrid network seems impor- according to standard methods. 1,2-Diaminocyclohexane
tant. It is modified by the addition of TEOS in the prepa- (mixture of cis and trans isomers), (3-chloropropyl)trieth-
ration step but does appear to vary according to the pro- oxysilane and the ketones: acetophenone, 2-methoxyaceto-
portion of rhodium complex. phenone, 3-methoxyacetophenone, and 4-methoxyaceto-
BRh-0 proved to be the catalyst leading to the high- phenone were purchased from Aldrich (Milwaukee, WI).
est selectivities among all those studied. We thus studied n-Nonaphenone, isobutyrophenone, 2-methylacetophe-
the case of the reduction of various prochiral ketones none, and methyl-2-naphthylketone were purchased from
(Scheme 9). Acros and methyl-1-naphthylketone from Fluka (Milwau-
Selectivities ranging from 4098% were observed in the kee, WI). Silica Gel 60 (Lichroprep RP-2) with a specific
hydrogen-transfer reaction, depending on the nature of the surface area of 500 m2g1 was purchased from Merck
aromatic and the alkyl substituents (Table 3). Hindered (Darmstadt, Germany).
ketones lead to enantioselectivities as high as 98%; how- 1
H, 13C and 29Si NMR spectra in solution were recorded
ever the reduction is slow and a low conversion was ob- on Bruker AC-200 and AC-250 spectrometers at room tem-
served. perature using deuterated chloroform as solvent, TMS as
internal reference 13C, and 29Si solid state NMR spectra
were obtained from Bruker FT-AM 200 or FT-AM 400 spec-
trometers using cross-polarization and magic angle spin-
ning techniques (CP-MAS) and TMS as reference for the
chemical shifts. Chemical shifts are given in ppm. Mass
Scheme 9. Hydrogen-transfer reduction of prochiral ketones with BRh-0. spectra were measured on a JEOL MS-DX 300 mass spec-

trometer. Optical rotations were obtained using a Perkin- +, NBA) 523 [M+H]+. Anal. Calcd. for C24H54N2O6Si2: C,
Elmer (Norwalk, CT) polarimeter 241. Enantiomeric ex- 55.14; H, 10.41; 5.35. Found = C, 54.56; H, 10.30; N, 5.30.
cesses (ee) were determined by HPLC analysis using a
chiral cellulose stationary phase (Chiralcel OD column) Preparation of Solid Gel M-5
with hexane/2-propanol (9:1) as mobile phase (flow of 1 In a Schlenk tube were successively added 0.9 g of M
ml/min1) and a UV detector at 250 nm. A Cary 1E appa- (2.8 mmol), 2.9 g of Si (OEt)4 (14 mmol), and 17 ml of dry
ratus was used for recording the UV-visible electronic ab- ethanol. The solution was stirred at room temperature and
sorption spectra of the metallic complexes in solution. A 600 l of water (32.2 mmol) were added. An opaque gel
Perkin-Elmer Lambda 14 equipped with an integrated formed after 20 min. This gel was aged for 1 week and was
sphere was used for the UV-visible spectra of the solid then ground in a mortar. The white powder was washed
materials, with barium sulfate as reference. with ether, filtered, and dried under vacuum for 24 h at
Nitrogen surface area measurements were performed 60C. 1.5 g of xerogel M-5 were obtained.
according to the BET method, at 77 K with a Micromeritics FT-IR (KBr, cm1): Si-O = 1061; C-H = 2865, Si-OH
Gemini 2375 equipment. Elemental analyses of the molecu- =3409. 13C CP-MAS NMR: 8 (CH2-Si), 18 (CH3) 20-40
lar precursors and the solid materials were carried out by (CH2, (cyc), Si-CH2- CH2), 50-68 (O- CH2, N- CH2, N- CH). 29Si
the Service Central dAnalyse du CNRS at Vernaison, CP-MAS NMR: -68 (T3), -102 (Q3), -109 (Q4). Anal.
France. EDX (energy dispersive X-ray) measurements Found: C, 23.77; H, 4.90; N, 4.51; Si, 29.5 corresponding to
were also performed to determine the rhodium/chlorine/ C11.3H27.8N1.9O13.3Si6. Surface area (BET) = 280 m2 g1.
silicon atomic percent using a Cambridge instrument-
stereoscan-360 scanning electronic microscope (SEM) Preparation of Complexed Solid Gel MRh-2
equipped with an EDS-Link AN 10000 probe. In a Schlenk tube were successively introduced 0.5 g of
The resolution of trans-1,2-diaminocyclohexane was car- M (1.57 mmol), 0.38 g of [Rh(cod)Cl]2 (0.785 mmol) and 5
ried out as described in the literature.53 ml dry ethanol. The yellow solution was stirred for 20 min
at room temperature and 0.75 g of Si (OEt)4 (3.14 mmol)
Synthesis of N-[(triethoxysilyl)propyl]-()-(1R,2R)- followed by 150 l of water (8.63 mmol) were added. A
1,2-diaminocyclohexane, M yellow transparent gel was obtained after 20 min and was
left for 1 week aging. The gel was powdered and constantly
In a glass tube were introduced 10.5 g (92 mmol) of
washed with THF for 20 h by means of a soxhlet apparatus.
()-(1R,2R)-diaminocyclohexane and 11 g (46 mmole) of
The mixture was filtered at room temperature for 24 h
(3-chloropropyl)triethoxysilane. The tube was sealed and
yielding 0.6 g of MRh-2. FT-IR (KBr, cm1): Si-O = 1075;
placed in an oil bath at 87C. A white precipitate formed
C-H = 2866, 2940; Si-OH = 3406. Anal. by E.D.X (Atomic%):
after 0.5 h. The reaction mixture was left at that tempera-
Si, 59.7; Rh, 20.5 and Cl, 19.8. Surface area (BET) = 3
ture overnight (18 h). The sealed tube was opened and the
white solid was rinsed with freshly distilled pentane (3 25
ml). The solvent was pumped off from the filtrate and the Preparation of Complexed Solid Gel MRh-5
remaining yellowish solution was distilled, yielding a col-
The same procedure as above was used with: 0.83 g (2.6
orless liquid corresponding to M (70%). B.P. (0.02 mm Hg)
mmol) of M; 0.64 g (1.3 mmol) of [Rh(cod)Cl]2; 2.7 g (13
= 105C. []D20 = 50.6 (c 1.4 ; THF). 1H NMR (CDCl3)
mmol) of Si(OEt)4, 538 l (29.9 mmol) of H2O; 15.6 ml of
0.6-0.7 (m , 2H); 1.2 (t, 9H); 1.3-2 (m , 10H); 2.1-2.5 (m ,
dry EtOH. The yellow gel formed after 10 min and after the
3H); 2.6-2.7 (m , 1H); 13C NMR 63.9, 58, 55, 50, 36.1, 31.5,
usual work-up 1.8 g yellow powder of MRh-5 was obtained.
25.3, 23.8, 18.2, 8; 29Si NMR -44.8. Mass spectrum (FAB+;
FT-IR same as above. 13C CP-MAS NMR: 8.1 (CH2-Si); 18
NBA): 319 [M+H]+. Anal. Calcd. for C15H34N2O3Si: C,
(CH3); 20-40 (CH2 (cyc), Si-CH2-CH2, CH2-CH=CH); 50-68
56.56; H, 10.76 ; N,8.79. Found: C, 55.98; H, 10.68; N, 8.56.
(CH2-O, N- CH2, N- CH); 70-90 (CH= CH). 29Si CP-MAS
NMR: ppm -66 (T3), -103 (Q3), 110 (Q4). Anal. Found: C,
Synthesis of
24.24; H, 4.4; N, 3.02; Si, 21.8; Cl, 3.6; Rh, 10.8 correspond-
ing to C15.6 H33.7 N1.7O15.7Si6Rh0.8Cl0.8. Elemental analysis
1,2-diaminocyclohexane, B
by E.D.X. (Atomic%): Si, 75.58; Rh 12.25; Cl, 12.17. Surface
In a glass tube were introduced 3 g (9.4 mmol) of M and area (BET): 224 m2 g1.
1.13 g (4.7 mmol) of (3-chloropropyl)triethoxysilane. The
tube was sealed at 110C. After 18 h, the tube was cooled Preparation of Complexed Solid Gel MRh-GS
to room temperature and opened. The pale brown residue This material was prepared in three steps from commer-
was extracted with freshly distilled pentane (3 25 ml) and cial silica.
the solution was filtered. The solvent was eliminated in Step 1: activation of silica. Four g of silica were intro-
vacuo leaving a brown viscous liquid corresponding to B. duced in a round-bottom flask equipped with a reflux con-
Attempts to purify B either by distillation or by chroma- densor; 20 ml of concentrated HCl (36%) was added and
tography failed and led to the decomposition of the prod- the mixture was refluxed for 4 h. The solution was filtered
uct. Yield = 60%. []D20 = 46.6 (c 1.2; THF); 1H NMR and the white powder was washed with distilled water until
(CDCl3) 0.6-0.7 (m, 4H); 1.2 (t, 18H); 1.4 -1.7 (m, 12H); neutral pH was attained. The solid was again washed with
2-2.1 (m, 4H); 2.6 (m, 2H). 13C NMR 61.3 , 58, 49.7, 31.5, acetone (3 times) and dried under vacuum at 180C for
24.9, 23.5, 18, 7.8; 29Si NMR 44.9. Mass Spectrum (FAB 24 h.

Step 2: grafting of M on the activated silica. In a 50 ml NMR similar as above. Anal. by E.D.X (Atomic%): Si, 66.8;
round-bottom flask were introduced successively 20 ml of Rh, 16.8; Cl, 16.4. Surface area (BET) = 6 m2 g1.
anhydrous toluene, 3 g of activated silica and 2 g (6.3
mmol) of M. The solution was refluxed for 1 day. The Preparation of Complexed Solid Gel BRh-1
solution was filtered and the solid was washed with acetone The same procedure as for gel BRh-0 was used except
and dried under reduced pressure at 60C. 4.48 g of the that 1 molar equivalent of Si(OEt)4 to bifunctional diamine
material were obtained. FT-IR (KBr, cm1): Si-O = 1178; derivative, B, was added to the mixture before hydrolysis.
C-H = 2872; Si-OH = 3409. 29Si CP-MAS NMR ppm -66 0.5 g (0.95 mmol) of B; 0.23 g (0.475 mmol) of [Rh-
(T3); -103 (Q3); -111 (Q4). Anal. Found: C, 9.60; H, 1.95; N, (cod)Cl]2; 0.2g (0.95 mmol) of Si(OEt)4; 86 l (4.75 mmol)
1.85; Si, 37.35 corresponding to C6.6H16N1.1O25.5Si11. of water; 3 ml of dry ethanol. A yellow transparent gel
Step 3: complexation with [Rh(cod)Cl]2. In a small formed after 2.5 h and after work-up 0.47 g of a yellow
Schlenk tube 1 g (0.6 meq NH/g) of the above functional- powder was obtained. The FT-IR and 13C CP-MAS NMR
ized silica was mixed with 0.14 g (0.3 mmol) of [Rh- are similar to those of gel BRh-0. 29C CP-MAS NMR: 65
(cod)Cl]2 in 2 ml of dry ethanol. The mixture was stirred (T3); 102 (Q2); 109 (Q4). Anal. by EDX (Atomic%): Si,
for 1 day under nitrogen atmosphere at room temperature. 59.6; Rh, 20.5; Cl, 19.8. Surface area (BET): 3 m2 g1.
The solution was filtered and the solid was dried under
reduced pressure at room temperature for 16 h, leading to Preparation of Complexed Solid Gel BRh-3
a yellow powder (1.1 g). FT-IR (KBr, cm1): Si-O = 1096; The same procedure as above was used with: 0.37 g (0.7
C-H = 2865; Si-OH =3463. 29Si CP-MAS NMR: -66 (T3); mmol) of B; 0.173 g (0.35 mmol) of [Rh(cod)Cl]2; 0.4 g (2.1
-103 (Q3); -111 (Q4). Anal. by E.D.X. (Atomic%): Si, 83.7; mmol) of Si(OEt)4; 100 l (6.3 mmol) of water; 3.5 ml of dry
Rh, 8.7; Cl, 7.6. ethanol. A pale yellow gel formed after 20 min leading to a
yellow powder (0.34 g) after the usual work-up. The FT-IR,
Preparation of Solid Gel B-0 CP-MAS (13C and 29Si) spectra are similar to those of gel
In a Schlenk tube 0.64 g (1.2 mmol) of B was solubilized BRh-1. Anal. by EDX (Atomic%): Si, 75.0; Rh, 14.6; Cl, 14.4.
with 1.2 ml of dry ethanol at room temperature. 660 l (3.66 Surface area (BET): 11 m2 g1.
mmol) of water was added. A transparent gel formed within
10 min and was aged for 1 week. The gel was powdered, Hydrogen-Transfer Reduction of Acetophenone with M
washed with ether, filtered, and dried under reduced pres- A solution of M (36.8 mg, 0.01 mmol), [Rh(cod)Cl]2
sure at 60C for 16 h. A white powder (0.2 g) was obtained. (27.7 mg, 0.056 mmol) and KOH (10 mg, 0.17 mmol) in 20
FT-IR (KBr, cm1): Si-O = 1061; C-H = 2871, 2943; Si-OH ml of degassed 2-propanol was introduced in a two-necked
=3414.13C CP-MAS NMR: 8.1 (CH2-Si); 17.2 (CH3); 20-40 flask equipped with a magnetic stirrer. The mixture was
(CH2 cyc, Si CH2- CH2); 58 (CH2-O); 50-58 (CH-N). 29Si stirred for 0.5 h under nitrogen atmosphere at room tem-
CP-MAS NMR: ppm broad signal -50 to -75 (T2 and T3). perature to allow the formation of the rhodium/diamine
Anal. Found: C, 48.54; H, 8.34; N, 9.04; Si, 18.30 corre- catalyst. The formation of the latter was confirmed by UV-
sponding to C12.24 H25.4 N1.98 O3.03 Si2. Surface area (BET) visible analysis. Acetophenone (1.35, 11.3 mmol) was then
= 20 m2 g1. added and the reaction was monitored by capillary gas
chromatography and the ee measured by HPLC using a
Preparation of Complexed Solid Gel BRh-0 Daicel chiracel OD column. After 5 d 95% conversion was
In a Schlenk tube 0.43 g (0.82 mmol) of B was stirred obtained. The reaction mixture was filtered and the solvent
with 0.2 g (0.41 mmol) of [Rh (cod)Cl]2 in 0.8 ml of dry was evaporated. The residue was subjected to column
ethanol at room temperature for 20 min. Fifty l (2.46 chromatography on silica gel (eluent: toluene/acetone 9:1)
mmol) of water was then added. A yellow transparent gel to give pure 1-phenylethanol. (ee = 14%, yield = 88%).
formed after 1 h and after 1 week aging the gel was ground
and washed with THF by means of a soxhlet apparatus for Hydrogen-Transfer Reduction of Acetophenone with B
20 h. After filtration and drying under reduced pressure at The same procedure as above was performed with the
room temperature, a yellow powder (0.5 g) was obtained. same amount of [Rh(cod)Cl]2 KOH, 2-propanol, acetophe-
FT-IR (KBr, cm1): Si-O = 1126; CH = 2860, 2931; Si-OH none, and B (60 mg, 0.01 mmol). 95% conversion was ob-
= 3409. 13C CP-MAS NMR: 8.1 (CH2-Si); 17.2 (CH3); 20-40 tained after 5 d. The same work-up gave pure 1-phenyletha-
(CH2 cyc, Si CH2-CH2, CH2H=CH); 50-68 (CH2-O, N- CH2, nol (ee = 25%, yield = 80%).
N-CH); 70-90 (CH=CH). 29Si CP-MAS NMR: broad signal
50 to 75 (T2 and T3). Anal. Found: C, 41.19; H, 6.89; N, General Procedure for the Hydrogen-Transfer
4.47; Si, 9.75; Cl, 6.66; Rh, 16.05 corresponding Reduction of Acetophenone with the Solid Materials
to C19.8H39.4N1.8O5.4Si2Rh0.9Cl1.1. Surface area (BET) = 5 In a two-necked flask, solid gel BRh-0 (5.34 mg, 0.083
m2 g1. mmol) corresponding to 1.64 103 equivalent of rhodium
per gram of solid, KOH (14 mg, 0.25 mmol) and 20 ml of
Preparation of Complexed Solid Gel B1/2Rh-0 2-propanol were stirred for 0.5 h under nitrogen atmo-
The same procedure as above was performed with: 0.6 g sphere at room temperature. Acetophenone (1 g, 8.3
(1.14 mmol) of B; 0.1 g (0.285 mmol) of [Rh(cod)Cl]2; 62 l mmol) was added and the reaction was monitored by cap-
(3.42 mmol) of water; 1.14 ml of dry ethanol. A yellow illary gas chromatography. After 5 d (75% conversion) the
powder (0.63 g) was obtained. FT-IR, 13C and 29Si CP-MAS solution was filtered and purification by column chroma-

tography on silica gel as previously described afforded the hydrogenation of some unsaturated hydrocarbons in the liquid
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