Silane deuteration catalyzed by ruthenium bis(dihydrogen) complexes or simple metal salts

Article abstract of DOI:10.1002/adsc.201300902

The deuteration of a diverse group of silanes: alkyl-, aryl-, alkoxy- and chlorosilanes, siloxane and silazane, under an atmosphere of dideuterium (D ₂) was explored with ruthenium bis(dihydrogen) dihydride complexes and hydrated metal salts. Deuterium incorporation of greater than 97% for the silanes O(SiMe₂H)₂, Et₃SiH, (EtO) ₃SiH and Me₂ClSiH was possible with 0.1 mol% of the ruthenium complex [RuH₂(η²-H₂) ₂(PCyp₃)₂] [0.05 mol% for O(SiMe ₂H)₂] when catalysis was conducted in the neat silane at 30°C under 1 bar of D₂ for 3.5 h. The air-stable ruthenium trichloride salt RuCl₃xH₂O was also an efficient catalyst for the deuteration of O(SiMe₂H)₂ and Et ₃SiH; deuterium incorporations for the two silanes of 93% and 90%, respectively, were possible under the same conditions as for [RuH ₂(n²-H₂)₂(PCyp₃) ₂] with 0.1% catalyst loading. Hydrogendeuterium exchange of O (SiMe₂H)₂ catalyzed by the rhodium trichloride (RhCl ₃xH₂O) and iridium trichloride (IrCl ₃xH₂O) was similarly efficient as with RuCl ₃xH₂O although catalytic alacrity dropped for Et ₃SiH.

Full text of DOI:10.1002/adsc.201300902

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DOI: 10.1002/adsc.201300902
Silane Deuteration Catalyzed by Ruthenium Bis(dihydrogen)
Complexes or Simple Metal Salts
Katharine A. Smart,a Emmanuelle Mothes-Martin,a Tatsuro Annaka,a,b
Mary Grellier,a and Sylviane Sabo-Etiennea,*
a
CNRS, LCC (Laboratoire de Chimie de Coordination), BP44099, 205 route de Narbonne, and Universitꢀ de Toulouse,
UPS, INPT, F-31077 Toulouse, France
E-mail: sylviane.sabo@lcc-toulouse.fr
On leave from Department of Chemistry, Faculty of Science and Graduate School of Science and Engineering, Saitama
b
University, 255 Shimo-okubo, Sakura-ku, Saitama 338-8570, Japan
Received: October 18, 2013; Revised: December 4, 2013; Published online: February 20, 2014
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300902.
Abstract: The deuteration of a diverse group of si-
lanes: alkyl-, aryl-, alkoxy- and chlorosilanes, silox-
ane and silazane, under an atmosphere of dideuteri-
um (D2) was explored with ruthenium bis(dihydro-
gen) dihydride complexes and hydrated metal salts.
Deuterium incorporation of greater than 97% for
ods for the addition of deuterium to molecules exploit
well-established routes modified by the use of deuter-
ated reagents. Homogenous metal catalysis is an in-
valuable tool for deuteration, greatly enhancing the
À
scope of E H (E=H, C, Si) bonds which may be suc-
À
cessfully transformed into E D bonds.
the silanes O
Me2ClSiH was possible with 0.1 mol% of the ruthe-
nium complex [RuH2A 2A(PCyp3)2] [0.05 mol%
(h2-H2)
for O(SiMe2H)2] when catalysis was conducted in
the neat silane at 308C under 1 bar of D2 for 3.5 h.
The air-stable ruthenium trichloride salt
RuCl3·xH2O was also an efficient catalyst for the
deuteration of O(SiMe2H)2 and Et3SiH; deuterium
A
Hydrosilylation is a common route for the reduc-
tion of unsaturated groups and could be exploited for
the addition of deuterium to an organic substrate.[2]
Hydridosilanes are also useful for the reduction of
carbon-halogen bonds including hydrodefluorina-
tion.[3] Deuterosilane could therefore be used to bring
about labeling in a highly selective manner in a variety
of molecules. The standard method for silane deutera-
tion is the reduction of a silicon-halogen bond by
NaBD4 or LiAlD4.[4] An effective route bypassing the
stoichiometric generation of a halide salt would be
C
CHTUNGTRENNUNG
ACHTUNGTRENNUNG
AHCTUNGTRENNUNG
incorporations for the two silanes of 93% and 90%,
respectively, were possible under the same condi-
tions as for [RuH
lyst loading. Hydrogen–deuterium exchange of
(SiMe2H)2 catalyzed by the rhodium trichloride
(h2-H2)
2ACHTUNGTERNNUG 2ACHTUNTGERN(NUGN PCyp3)2] with 0.1% cata-
À
highly beneficial. An early example of catalytic Si H
O
A
exchange with an external deuterium source was
given by Curtis and co-workers.[5] The first study into
the catalytic deuteration of hydridosilanes with D2 by
(RhCl3·xH2O) and iridium trichloride (IrCl3·xH2O)
was similarly efficient as with RuCl3·xH2O although
catalytic alacrity dropped for Et3SiH.
the rhodium dimer [RhHACHTNUTRGNENG(U dipe)]2 was reported by
Fryzuk and co-workers in 1991 although no details of
the catalyst loading or D incorporation were provid-
ed.[6]
Keywords: catalysis; deuterium; hydrides; silicon;
transition metals
À
The selective deuteration of the Si H bonds of
1,1,3,3-tetramethyldisilazane, HN
(SiMe2H)2, catalyzed
by the bis(dihydrogen) ruthenium complex [RuH
H2)2A(PCy3)2], 1, (Cy=cyclohexyl) was investigated by
The incorporation of isotopic labels into chemical our group in 2005 (Scheme 1).[7] The deutero product
compounds is a simple yet powerful technique for HN(SiMe2D)2 was subsequently employed for a solid-
2ACHTUNGTRENNUNG
(h2-
CTHUNGTRENNUNG
AHCTUNGTRENNUNG
2
probing molecular transformations, enhancing spec- state H NMR spectroscopy study of the molecular
À
troscopic studies and obtaining revealing kinetic pa- dynamics of the SiMe2D moiety grafted to various
rameters.[1] Methods for selective H/D exchange are forms of silica.[8] In 2010, Carmona and co-workers re-
valuable to develop considering the profundity of re- ported a highly efficient rhodium-catalyzed prepara-
actions proceeding by hydrogen transfer and the om- tion of deuterated and even tritiated silanes under an
nipresence of H NMR spectroscopy. Common meth- atmosphere of D2 or T2.[2b,9] It was possible to prepare
1
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Katharine A. Smart et al.
À
Initial testing of the feasibility of Si H/D exchange
for Et3SiH catalyzed by 2 was carried out with
1 mol% catalyst loading in C6D6, under an atmos-
phere of D2 (1 bar). The reaction mixture was stirred
vigorously at 308C to promote solution homogeneity
and convection of reagents. To favor the equilibrium
between protio- and deuterosilane, the reaction mix-
ture was frozen and the atmosphere of D2 refreshed
by evacuation followed by reapplication of the gas
(see the Experimental Section). Deuterium incorpora-
tion of 92% was gauged after a reaction time of 3.5 h
Scheme 1. Deuteration of HNACHTNUGRTNEUNG
(SiMe2H)2 by D2 with 1.[7]
1
from H NMR spectroscopy by integration of the re-
À
sidual Si H signal and the ethyl groups. Additional
2
characterization by H and 29Si NMR together with
IR spectroscopic analyses was conducted. The effect
of changing the pressure of D2 and the catalyst load-
ing was investigated and Table 1 displays the incorpo-
ration of deuterium into the silane.
When the amount of catalyst was halved to
0.5 mol% and the reaction time doubled to 6.5 h,
95% deuterium incorporation was achieved (entry 2,
Table 1). Increasing the pressure of deuterium from
1 to 3 bar had essentially no effect on the deuterium
incorporation (entry 3, Table 1). When the experiment
was conducted in the absence of D2, C6D6 was able to
Scheme 2. Deuteration of Et3SiH catalyzed by a RhACTHUNTGRNEUNG(III)
complex.[9a]
Et3SiD, Me2PhSiD and Ph2SiD2 on a scale of several act as a deuterium source, 12% deuterium incorpora-
grams with very low catalyst loading (for example: tion was observed (entry 4, Table 1). Considering that
À
0.01% catalyst in neat Et3SiH at 508C, 0.5 bar D2, C D activation of C6D6 by 2 has previously been
>99% D incorporation) (Scheme 2). The alacrity of demonstrated, it is possible to account for the minor
[12]
À
À
À
Si H/D exchange is accounted for by the facility of conversion of Si H to Si D. When D2 (1 bar) was
H/D-exchange observed for sp3-hybridized C H applied to a mixture of Et3SiH and C6D6 in the ab-
groups of the phosphine xylyl groups of the rhodium sence of a catalyst, no deuterium incorporation was
À
complex.[9a] In 2011, Nolan and co-workers found that observed (entry 5, Table 1).
the iridium-N-heterocyclic carbene complex, [IrCl
(I-t-
The deuteration of five other silanes HNCAHTUNGTRENUN(GN Me2SiH)2,
Bu’)2], was a more efficient catalyst than the analo-
OACHTNUTGERNG(NUN SiMe2H)2, (i-Pr)2ClSiH, (EtO)3SiH and Me2ClSiH,
gous rhodium complex, and 94% deuterium incorpo- was also investigated. The same experimental proce-
ration for Et3SiH with a low catalyst loading of dure was followed as outlined for Et3SiH. Deuterium
0.01 mol% was achieved (CD2Cl2, 0.5 atm D2, 3 h).[10] incorporation greater than 95% was achieved with 0.1
Following our initial investigation of the deutera- or 0.05 mol% 2 (entries 6–9, Table 1). As previously
tion of 1,1,3,3-tetramethyldisilazane and with impetus reported, in the case of HN
provided by the more recent results in this area, we
ACHTUGNTRENUN(GN Me2SiH)2, very selective
decided to study silane deuteration with [RuH
H2)2A(PCyp3)2], 2, (Cyp=cyclopentyl) the tricyclopen-
(h2-
2ACHTUNGTRENNUNG
Table 1. Deuteration of silanes in C6D6 with 2 after 3.5 h at
308C.
CHTUNGTRENNUNG
tylphosphine analogue of 1. The two complexes ex-
hibit distinct behavior due to the different sizes of the
cycloalkyl rings.[11] A thorough study of the deutera-
tion processes of 2 has recently been presented.[12]
Entry Silane
D2
[bar]
Catalyst
[mol%]
Dincorp
[%]
1
2
3
4
5
Et3SiH
Et3SiH
Et3SiH
Et3SiH
Et3SiH
1
1
3
0
1
1
1
1
1
1
1.0
92
95
93
12
0
98
97
95
99
99
2
0.5[a]
1.0
Combining neutron diffraction and H NMR, it was
possible to demonstrate that together with exchange
of the hydride and dihydrogen ligands with deuteri-
1.0
0
À
um, C H/D exchange at the cyclopentyl ligand could
6
7
8
9
HN
(SiMe2H)2
(i-Pr)2ClSiH
(EtO)3SiH
Ph3SiH
(Me2SiH)2
0.05
0.05
0.10
0.10
1.0
be achieved depending on the conditions. We now
present the catalytic deuteration of a range of silanes
by the dihydride bis(dihydrogen) ruthenium com-
plexes 1 and 2, and disclose the ability of the hydrated
salts MCl3·xH2O (M=Ru, Rh, Ir) to also act as cata-
lyst precursors under very mild conditions.
OACHTUNGTRENNUNG
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
10
[a]
Reaction time 6.5 h.
760
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Silane Deuteration Catalyzed by Ruthenium Bis(dihydrogen)
The high deuterium incorporation of 97% for
Et3SiH (entry 1 Table 2) indicates that 2 is a very
À
active catalyst for Si H/D exchange in the absence of
solvent. It is interesting that a greater extent of
Et3SiH deuteration may be achieved with lower cata-
lyst loading when C6D6 is not present despite evi-
dence that deuterium may be transferred from C6D6
to the silane (entry 4 Table 1). It is possible that in
Scheme 3. Procedure for the catalytic deuteration of neat si-
lanes with 2 under an atmosphere of D2.
À
C6D6, a pathway involving C D bond activation may
À
D-incorporation was achieved with no H/D exchange compete with Si H/D exchange. The solubility of D2,
at the NH site.[7] The silane deuteration study con- DH and H2 in C6D6 and the neat silane might also be
ducted by Nolan and co-workers reports 98% deuteri- important factors. There is essentially no difference
um incorporation for triethoxysilane with 1 mol% between the deuterium incorporation for O
ACHTUNGTRNE(NUNG SiMe2H)2
[IrCl(I-t-Bu’)2] loading and a reaction time of three obtained with and without C6D6, 97% (entry 7
ACHTUNGTRENNUNG
hours although under the same conditions, only 48% Table 1) and 99% (entry 4 Table 2), respectively. Half
À
deuterium incorporation was achieved for diisopro- the amount of catalyst, per Si H bond, is required to
pylchlorosilane.[10] We also tested H2SiPhMe which bring about 99% deuteration of
OACTHNGUETR(UNNG SiMe2H)2,
led to complete H/D exchange but with extensive re- 0.05 mol% (entry 4 Table 2), than was required for
distribution reactions as already observed when ex- 97% deuteration of Et3SiH, 0.1 mol% (entry 1
posing such a secondary silane to a bis(dihydrogen) Table 2). OACTHNUGRTNE(UNG SiMe2H)2 is distinct from Et3SiH because
ruthenium complex.[13] D2SiPhMe, DSiPh2Me and it features two Si H bonds. Perhaps a cooperative
DSiMe2Ph were obtained in a 3:1:0.1 ratio. Finally, effect for deuteration of both Si H bonds of the same
À
À
excellent deuterium incorporation was also achieved
O
U
in the case of the arylsilane HSiPh3 (entry 10, complex [RuH2{(h2-HSiPh2)2O}
ACHTNUGTRNEUNG(PCy3)2], 3, was re-
Table 1).
Considering that many silanes are liquids, the feasi-
bility of solvent-less Si H/D exchange was investigat- two Si H bonds. Presumably exchange with deute-
ed (Scheme 3). Eliminating the need for solvent rium could occur cooperatively for the coordinated
would substantially reduce the cost of the process if it Si H bonds. Considering the similarity between 1 and
were conducted on a large scale. Furthermore, the 2, it would seem rational that the complexes undergo
ported from the reaction of 1, with two equivalents of
2
À
O
(SiMe2H)2 featuring h -Si H coordination of the
[14]
À
À
À
isolation of the deuterated silanes is more facile in similar reactivity with OACHTNUGTRENNUNG
the absence of a solvent. As for the reactions carried equivalents of OACHTGNUTRENNUNG
1
out in C6D6, the homogenous solution of silane and 2 suspension of 2, H and 31P NMR spectra collected
was frozen in the Fischer–Porter vessel and the at- from the resulting grey powder were similar to those
mosphere of argon removed under vacuum. The mix- of 3. A single broad singlet was observed at d=À9.80
1
ture was allowed to melt and D2 (1 bar) was applied in the hydride region of the H NMR spectrum for
to the stirred solution at 308C. The atmosphere inside the product of the reaction of OACHTUNRTGNEUNG(SiMe2H)2 with 2 and
the vessel was refreshed three times during the reac- a broad signal in the 31P NMR spectrum at d=42.7.
tion. The silane and catalyst were stirred together at For 3, the corresponding data are d=À9.48 for the
308C under an atmosphere of D2 for a total time of 1H NMR of the hydride and d=49.9 for the 31P NMR
3.5 h. The results are presented in Table 2.
chemical shift.[14] Further analysis of the product of
the reaction of O
ACHTUGNRTEN(NUGN SiMe2H)2 with 2 is underway.
When O(SiMe2H)2 was stirred under an atmos-
AHCTUNGTRENNUNG
phere of D2 in the absence of 2, 6% deuterium incor-
poration was identified (entry 8, Table 2). Despite
careful washing of the reaction vessel and stir bar
with aqua regia to eliminate traces of ruthenium
before each catalytic run, it appears that partial acti-
Table 2. Deuteration of neat silanes with 2 after 3.5 h at
308C.
Entry
Silane
Catalyst [mol%]
Dincorp [%]
1
2
3
Et3SiH
Et3SiH
Et3SiH
0.10
0.05
0
97
75
0
À
vation of Si H occurs by some means. No deuterium
incorporation was observed when Et3SiH was stirred
with 1 bar D2 in the absence of an added catalyst,
(entry 3, Table 2). Full deuteration of (EtO)3SiH (>
99%) was achieved in the neat silane with 0.10 mol%
catalyst loading (entry 9 Table 2), similar to the 99%
incorporation achieved in C6D6, (entry 9 Table 1). The
deuteration of Me2ClSiH was accomplished with
0.10 mol% loading and >99% deuterium incorpora-
4
5
6
7
O
G
0.0500
0.0100
0.0075
0.005
0
99
80
53
42
O
R
O
R
O
R
8
OC
6
9
10
G
0.10
0.10
> 99
> 99
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Katharine A. Smart et al.
Scheme 4. Preparation of a deuterated silazane compound.
Scheme 5. Procedure for the catalytic deuteration of neat
Et3SiH with RuCl3·xH2O under an atmosphere of D2.
tion (entry 10, Table 2). The reaction was conducted
on a relatively large scale (7 g) to prepare Me2ClSiD noteworthy that hydrolysis of the silanes was not ob-
for use as a reagent in the synthesis of a deuterated si- served in the presence of trace amounts of water
lazane compound (Scheme 4).
The ability of the PCy3 complex 1 to catalyze the the deuterium incorporation values by extension of
deuteration in neat Et3SiH and O(SiMe2H)2 was also the reaction time. For the study reported by Carmona
investigated. For O(SiMe2H)2, deuterium incorpora- and co-workers for the deuteration of Et3SiH, it was
bound to ruthenium. It might be possible to improve
AHCTUNGTRENNUNG
AHCTUNGTRENNUNG
tion of 99% was achieved with 0.05 mol% catalyst possible to achieve >99% deuterium incorporation
loading of 1 and 2. When 0.01 mol% of 1 was em- with 0.01 mol% catalyst loading after 24 h at 508C.[9a]
ployed, deuterium incorporation was 67% versus 80%
in the case of 2. In view of the relatively small differ- catalytic reaction with Et3SiH was investigated; it was
ences, a fuller study with 1 was not undertaken. thought that the phosphine might stabilize the catalyt-
The effect of added tricyclopentylphosphine on the
The studies of silane deuteration reported by Car- ically active species. However, the presence of two
mona, and Nolan have featured expensive air-sensi- equivalents of PCyp3 in the reaction vessel appears to
À
tive rhodium- or iridium-ligand complexes as cata- significantly hinder Si H/D exchange, 2% deuterium
A
lysts.[9a,b,10] In our system, even if ruthenium can be incorporation was observed. Perhaps the phosphine
À
considered as a cheaper metal, we are still faced with competes with Si H activation through coordination
the sensitivity problem of 1 and 2. The ability of the to ruthenium. The reaction with O
unelaborate salt RuCl3·xH2O to catalyze Si H/D ex- ducted in the presence of a drop of mercury as a test
change was thus examined as a robust route for the for the homogeneity of the process.[15] Deuterium in-
deuteration of silanes. The reactions were carried out corporation in the presence of mercury was 73%
in the same manner as described when 1 and 2 were (entry 5, Table 3) which does not discount the homo-
N
À
the catalysts. RuCl3·xH2O is not immediately soluble genous catalytic deuteration of
when mixed with Et3SiH or O(SiMe2H)2 however, RuCl3·xH2O.
after stirring for ca. 10 min at 308C the black solid The ability of RhCl3·xH2O and IrCl3·xH2O to cata-
OACTHNGUETR(UNNG SiMe2H)2 by
AHCTUNGTRENNUNG
suspended in the colorless liquid became a dark lyze the deuteration of silanes was also investigated
brown solution for each silane. The deuterium incor- and compared to the high deuterium incorporation
poration percentages are presented in Table 3. It was achieved with RuCl3·xH2O. Even if the rhodium and
possible to achieve high deuterium incorporation with iridium salts display similar activity for O
RuCl3·xH2O as the catalyst for both Et3SiH (entries 8 and 10 versus 3) the results are considerably
(Scheme 5) and O(SiMe2H)2. With 0.1 mol% catalyst different in the case of Et3SiH with only 6% of deute-
loading, 90% of Et3SiH (entry 1, Table 3) was deuter- rium incorporation at rhodium and no exchange at all
ACHTUNGTRNE(NUNG SiMe2H)2
AHCTUNGTRENNUNG
ated and 93% of OACHTNUTRGNE(NUG SiMe2H)2 (entry 3, Table 3). It is at iridium (entries 7 and 9, respectively, Table 3).
As for 1 and 2, the MCl3 series have a greater abili-
À
ty to catalyze Si H/D exchange in O
Et3SiH. It is possible that the presence of two Si H
G
À
Table 3. Deuteration of neat silanes with MCl3·xH2O (M=
Ru, Rh, Ir) after 3.5 h at 308C.
bonds in O
tion. The Karstedtꢂs catalyst, [{Pt
SiMe2)2O)}2m-(CH2 =CHSiMe2)2O], is industrially em-
ployed for hydrosilylation and features the coordina-
tion of vinylsiloxane to Pt.[16] Perhaps O
(SiMe2H)2 is
ACHTUNGTRENNUNG
Entry Silane
Catalyst
mol% Dincorp [%]
AHCTUNGTRENNUNG
1
2
3
4
5
6
7
8
9
Et3SiH
Et3SiH
OACHTUNGTRENNUNG
RuCl3·xH2O
RuCl3·xH2O
0.10
0.05
0.10
0.01
90
30
93
52
73
23
6
85
0
91
a ligand at the metal center when MCl3·xH2O is a cat-
alyst for deuteration and stabilizes the catalytically
active species. In the ruthenium case, it is noteworthy
OACHTUNGTRENNUNG
OACHTUNGTRENNUNG(SiMe2H)2 RuCl3·xH2O+Hg 0.10
Me2ClSiH
Et3SiH
that h2-coordination of O
ACHTUNGTRENNUNG
RuCl3·xH2O
RhCl3·xH2O
0.10
0.1
0.1
0.1
0.1
OT
AHCTUNGTRENNUNG
RuCl3·xH2O. A mechanistic investigation is in prog-
ress to explore such a pathway.
10
OG
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Silane Deuteration Catalyzed by Ruthenium Bis(dihydrogen)
2
Table 4. 1H and 29Si NMR (C6D6) and H NMR (C6H6) and infrared spectroscopic (neat) data for selected silanes and the
deuterated isotopomers [d (ppm), J (Hz), n (cmÀ1)].
Silane
1H (2H) NMR dSiH (dSiD
)
29Si NMR dSi
1JSi,H (1JSi,D
)
nSiH (nSiD)
Et3SiH
4.00 (3.90)
4.82 (4.82)[7]
5.06 (4.97)
4.68 (4.57)
4.92 (4.78)
0.13 (À0.38)
178 (27)
194 (29)
204 (31)
288 (36)
223 (34)
2100 (1530)
2119 (1539)[7]
2128 (1548)
2196 (1603)
2169 (1575)
HN
(SiMe2H)2
(EtO)3SiH
Me2ClSiH
(Me2SiH)2
À11.49 (À11.83)
À4.61 (À5.09)
À59.12 (À57.04)
11.40 (11.12)
O
ACHTUNGTRENNUNG
ACHTUNGTRENNUNG
In conclusion, it has been possible to achieve the mixture was frozen at À508C and the argon removed by ap-
plication of a vacuum for 20 s. The reaction mixture was al-
lowed to melt and the Fischer–Porter vessel placed in a ther-
mostatically controlled water bath at 308C. With the reac-
tion mixture stirring vigorously at 1300 rpm, D2 (1 bar over
the atmospheric pressure) was applied and the stirring main-
tained. After 1 h, the reaction mixture was again frozen at
À508C and the atmosphere inside the Fischer–Porter vessel
evacuated. After melting, returning to 308C, and recom-
mencing the stirring, the D2 (1 bar over the atmospheric
pressure) atmosphere was reapplied. The procedure of
catalytic deuteration of silanes with several transition
metal species. It was possible to achieve 99% deuteri-
um incorporation in neat O
[RuH2A 2A(PCyp3)2]. The same deuterium incor-
(h2-H2)
poration for O(SiMe2H)2 was also observed with
0.05 mol% [RuH2A 2A(PCy3)2] although the cata-
(h2-H2)
ACHTUNGTREN(NUNG SiMe2H)2 with 0.05 mol%
C
CHTUNGTRENNUNG
ACHTUNGTRENNUNG
C
CHTUNGTRENNUNG
lyst is less efficient at low loading. It is likely that
longer reaction times for the deuteration experiments
would enhance deuterium incorporation although op-
timization has not been studied. Extensive deuterium freezing, evacuating and reapplication of D2 was twice re-
peated, after 1 h and then after a further 45 min. After
a total time of 3.5 h, 1H NMR spectroscopic analysis was
employed to ascertain the incorporation of deuterium.
29Si{1H} NMR spectra were collected for characterization of
the deuterated silane products (see Table 4).
incorporation was also possible for Et3SiH, 97% with
0.1 mol% [RuH2A 2A(PCyp3)2]. The deuterated si-
C
CHTUNGTRENNUNG
lanes (EtO3)SiD and Me2ClSiD were also generated
in >80% isolated yields with deuterium incorpora-
tions of >99% following the same method on a scale
of several grams. The facile route to deuterosilanes
developed in this study was exploited in the prepara-
tion of a deuterated silazane from Me2ClSiD.
The experiments catalyzed by [RuH2ACHTNUTRGNENUG 2CAHUTNGTREN(NUGN PCyp3)2],
(h2-H2)
IrCl3·xH2O, RhCl3·xH2O and RuCl3·xH2O, conducted in the
absence of C6D6, were conducted in the same manner as
outlined above although the silanes were frozen with N2
(liquid).
The
RhCl3·xH2O and IrCl3·xH2O were also proficient
deuteration catalysts for O(SiMe2H)2. With 0.1 mol%
simple
hydrated
salts
RuCl3·xH2O,
AHCTUNGTRENNUNG
MCl3·xH2O, ca. 90% deuterium incorporation was
possible. In the case of Et3SiH only the ruthenium
salt is a good catalyst precursor (90% D incorporation
at 0.1 mol% loading versus 6% and 0% in the Rh and
Ir cases, respectively). These preliminary results sug-
gest that the use of sensitive and rather sophisticated
Acknowledgements
We thank the CNRS for support and Johnson Matthey plc
for the generous gift of the hydrated metal salts. KAS thanks
the French Ministry of Research for a PhD fellowship. TA
transition metal complexes for silane deuteration thanks Saitama University for the support through the
Kanryu exchange program.
might not always be necessary as successful catalysis
can also be achieved with MCl3·xH2O salts (M=Ru,
Rh, Ir), particularly in the case of ruthenium, the
cheapest metal of the series.
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