Hydrosilylation of non-1-ene with phenylsilane in the presence of yttrium and lutetium bisguanidinate hydride complexes

Article abstract of DOI:10.1007/s11172-010-0310-1

Some regularities of hydrosilylation of non-1-ene with phenylsilane catalyzed by yttrium and lutetium bisguanidinate hydride complexes {[(Me ₃Si)₂NC(NR)₂]₂Ln(μ-H)} ₂ (Ln = Y, Lu; R = Prⁱ, C

Full text of DOI:10.1007/s11172-010-0310-1

Russian Chemical Bulletin, International Edition, Vol. 59, No. 9, pp. 1765—1770, September, 2010
1765
Hydrosilylation of nonꢀ1ꢀene with phenylsilane in the presence
of yttrium and lutetium bisguanidinate hydride complexes
D. M. Lyubov, A. S. Shavyrin, Yu. A. Kurskii, and A. A. Trifonov
G. A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences,
49 ul. Tropinina, 603950 Nizhny Novgorod, Russian Federation.
Fax: +7 (831 2) 462 7497. Eꢀmail: trif@iomc.ras.ru
Some regularities of hydrosilylation of nonꢀ1ꢀene with phenylsilane catalyzed by yttrium
and lutetium bisguanidinate hydride complexes {[(Me3Si)2NC(NR)2]2Ln(μꢀH)}2 (Ln = Y, Lu;
R = Pri, Cy (Cy is cyclohexyl)) have been studied. The addition of PhSiH3 to the double bond
of nonꢀ1ꢀene in the presence of a {[(Me3Si)2NC(NPri)2]2Y(μꢀH)}2 complex has the first order
in olefin and zero order in phenylsilane. This indicates that the insertion of nonꢀ1ꢀene into the
Ln—H bond is a rate determining stage of the process, whereas the metathesis of the Ln—C σꢀbond
upon the action of phenylsilane proceeds rapidly. The first example of successive double alkylaꢀ
tion of phenylsilane with an olefin catalyzed by a rareꢀearth metal complex with the formation
of tertiary silane has been discovered.
Key words: hydrosilylation, alkenes, phenylsilane, organosilicon compounds, yttrium comꢀ
plexes, lutetium complexes, kinetics.
Hydrosilylation of unsaturated substrates catalyzed by
transition metal complexes is one of the most simple and
atomꢀsaving methods for the functionalization of olefins,1
selective organic synthesis (for example, of small cycles2),
as well as preparation of siliconꢀcontaining polymers.3 By
now, platinum complexes are the most widely studied
among catalysts of hydrosilylation of olefins.4—9 Howevꢀ
er, these catalysts have a number of disadvantages, in parꢀ
ticular, they do not provide high chemoꢀ and regioselecꢀ
tivity. For instance, when primary silanes RSiH3 are used
as the silylating agents4 the reaction proceeds with the
formation of a mixture of products of both hydrosilylation
(RR´SiH2, RR´2SiH, and RR´3Si) and hydration (R´H)
of olefins. Catalysts based on the light transition metꢀ
als,10,11 actinides,12 and rareꢀearth elements2,13—26 exhibit
considerably higher selectivity in the hydrosilylation proꢀ
cesses of olefins with primary and secondary silanes, howꢀ
ever, their lower activity, together with sensitivity to oxyꢀ
gen and air moisture (and frequently with thermal instaꢀ
bility), considerably limits their application. The first exꢀ
amples of the use of the sandwichꢀtype rareꢀearth element
alkyl complexes as catalysts in the hydrosilylation reacꢀ
tions were published27 in 1989. Results of subsequent studꢀ
ies confirmed the high potential2,26 of these compounds.
Earlier,2,26 using cyclopentadienyl derivatives as examples
it was demonstrated that the nature of the metal atom
coordination sphere can significantly affect the rate and
regioselectivity of hydrosilylation. For instance, going from
the biscyclopentadienyl ligand system to the ansaꢀbound
biscyclopentadienyl one and the use of a rareꢀearth metal
with larger ionic radius allowed one to significantly inꢀ
crease the rate and selectivity (addition according to
the Markovnikov rule) of hydrosilylation of αꢀolefins.15
Replacement of biscyclopentadienyl ligand system
with the ansaꢀbound cyclopentadienylphosphide one and
the use of a lutetium complex [Me2Si(C5Me4)(μꢀPCy)ꢀ
LuCH2SiMe3]2 (Cy is cyclohexyl) as the catalyst allow
one, retaining a high rate of hydrosilylation of hexꢀ1ꢀene
with phenylsilane, to change regioselectivity of the process
and exclusively obtain Markovnikov addition products.
At the same time, catalytic activity of related comꢀ
plexes containing no cyclopentadienyl ligands remains virꢀ
tually uninvestigated. Lately, a tendency for search of new
noncyclopentadienyl ligand systems has been outlined,28
which is aimed on the increase in stability of the rareꢀ
earth metal derivatives with retaining high reactivity, the
higher stability of catalysts to functional groups of subꢀ
strates, broadening a possibility of design of the metal
atom coordination sphere in the complex, as well as conꢀ
trol of catalytic activity of metal complexes and selectivity
of the processes. There are new reports on the synthesis of
the rareꢀearth metal alkyl and hydride complexes, stabiꢀ
lized by amide,23,29,30 silylamide,31 silanolate,32 amidiꢀ
nate,33 bisphenolate34 ligands, and all of them were sucꢀ
cessfully used as catalysts of hydrosilylation of olefins.
Earlier,35—37 we have reported on the synthesis of
new lanthanide bisguanidinate hydride complexes
{[(Me3Si)2NC(NR)2]2Ln(μꢀH)}2 (Ln = Y, Nd, Sm, Gd,
Yb, Lu, R = Pri; Ln = Y, Lu, R = Cy), which demonstratꢀ
ed high catalytic activity in polymerization and hydrosilyꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1718—1723, September, 2010.
1066ꢀ5285/10/5909ꢀ1765 © 2010 Springer Science+Business Media, Inc.

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Lyubov et al.
lation of olefins. The present work is devoted to the study
of kinetic regularities of hydrosilylation of nonꢀ1ꢀene with
phenylsilane upon catalysis with bisguanidinate hydride
complexes {[(Me3Si)2NC(NR)2]2Ln(μꢀH)}2 (Ln = Y, Lu;
R = Pri, Cy).
related to the second possible isomer were found in the
NMR spectra.
It should be noted that complexes 1—4 have proved
inactive in catalysis of hydrosilylation of styrene and norꢀ
bornene.
For the study of kinetic regularities of the hydrosilylaꢀ
tion reaction of nonꢀ1ꢀene with phenylsilane, yttrium bisꢀ
guanidinate hydride complex {[(Me3Si)2NC(NPri)2]2ꢀ
Y(μꢀH)}2 (1) has been chosen as a test catalyst. As it is
known, the lanthanide hydride complexes catalyze polyꢀ
merization of αꢀolefins,28,38 as well as dehydration—oligoꢀ
merization of primary silanes,15,31 that can complicate
study of the hydrosilylation reactions. In order to clarify
a possibility of occurring these side reactions in the system
nonꢀ1ꢀene—PhSiH3—complex 1, we studied a behavior
of each reagent in the presence of the catalyst. It was
found that complex 1 does not catalyze oligomerization of
nonꢀ1ꢀene and dehydration—oligomerization of PhSiH3
at room temperature in hexane or benzene. This allows us
to exclude a possibility of the side reaction to affect kinetic
characteristics of the hydrosilylation process with a high
degree of probability.
Results and Discussion
We found that yttrium and lutetium hydride complexꢀ
es {[(Me3Si)2NC(NR)2]2Ln(μꢀH)}2 (Ln = Y, R = Pri (1);
Ln = Lu, R = Pri (2); Ln = Y, R = Cy (3); Ln = Lu,
R = Cy (4)) containing diisopropyl and dicyclohexyl
guanidinate ligands catalyze hydrosilylation of nonꢀ1ꢀene
with phenylsilane and provide, together with the high rate
at room temperature, a high regioselectivity, exclusively
leading to the formation of antiꢀMarkovnikov addition
product.32
It is known2,13,14,20,26 that in hydrosilylation of olefins
catalyzed by the rareꢀearth metal alkyl and hydride derivꢀ
atives of metallocene series, a hydride complex is the acꢀ
tive catalytic species. In this case, depending on the size of
cyclopentadienyl ligand coordinated with the lanthanide
atom, both the monomeric and dimeric hydride complexꢀ
es can be the intermediates. In another words, dissociaꢀ
tion of usually dimeric hydride derivatives in a number of
cases is not a necessary prerequisite for the catalytic reacꢀ
tion to proceed.20 To study chemical properties of new
bisguanidinate hydride derivatives 1—4, it seemed interꢀ
esting to study some regularities (including kinetic) of the
hydrosilylation reaction of nonꢀ1ꢀene with phenylsilane
in their presence.
The rate of hydrosilylation of nonꢀ1ꢀene with phenylꢀ
silane in the presence of yttrium hydride complex 1 was
studied by 1H NMR spectroscopy. The reaction was perꢀ
formed at the molar ratio of substrates 1 : 1 in benzeneꢀd6
at 20 0.5 °C in the presence of 2 mol.% of complex 1
(C0
= C0
= 0.309 mol L–1). The reaction
nonꢀ1ꢀene
PhSiH
progress3was monitored by the decrease in the signal inꢀ
tensities corresponding to the SiH3 group of phenylsilane,
the olefin protons of nonꢀ1ꢀene, as well as by the increase
of the signal intensities of the silylene protons SiH2 in the
forming phenylnonylsilane.
Hydrosilylation of nonꢀ1ꢀene with phenylsilane in
the presence of complexes 1—4 was performed on a preꢀ
parative scale in hexane at room temperature with the
Kinetic curves were built based on the NMR spectroꢀ
scopic data, which show the change in concentrations of
the reaction mixture components versus time (Fig. 1).
These dependencies are linear in the ln[C/C0]—t coorꢀ
dinates, i.e., the reaction has the overall first order (Fig. 2).
Particular orders of the reaction in phenylsilane and
nonꢀ1ꢀene were determined using method of steadyꢀstate
concentrations. To determine the order in one of the reꢀ
agents, the reaction was performed in the presence of a
fiveꢀfold molar excess of another, that allowed us to neꢀ
glect the change in its concentration during the process.
It was found that the dependence of the concentration
of nonꢀ1ꢀene from time under these conditions is linear in
the ln[C]—t coordinates (Fig. 3). This fact is an evidence
that the reaction has the first order in nonꢀ1ꢀene.
molar ratio of substrates 1 : 1 (C0
= C0
=
PhSiH
nonꢀ1ꢀene
3
= 0.309 mol L–1) and 2 mol.% of the catalyst. It was
found that all four catalysts possess close activities and the
reactions come to completion within for ∼12 h.
The study of hydrosilylation products by NMR specꢀ
troscopy and GLC showed that for all the catalysts,
the reaction proceeds with exclusive formation of phenylꢀ
(nonꢀ1ꢀyl)silane, the antiꢀMarkovnikov addition product
(Scheme 1).
Scheme 1
It turned out that the reaction has the zero order in
phenylsilane, since the dependence of the concentration
of phenylsilane from time is a straight line (Fig. 4).
Based on the fact that the reaction has the zero order
in PhSiH3 and its rate does not depend on its concentraꢀ
tion, it can be concluded that the rate determining stage of
the process is the insertion of nonꢀ1ꢀene into the Y—H
This is confirmed by the fact that in the 1H and 13C{1H}
NMR spectra of the reaction products, all the groupings
of the product are represented by a single set of signals.
The protons on the silicon atom SiH2 are found as a triplet
at δ 4.39 (3JH,H = 3.6 Hz), resulting from the splitting on
two methylene protons of the alkyl substituent. No signals

Lanthanide hydrides in hydrosilylation
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1767
[C]/mol L–1
[C]/mol L–1
a
b
0.3
0.3
0.2
0.1
0.2
0.1
2
4
6
8
10
12
14
t/h
2
4
6
8
10
12
14
t/h
Fig. 1. Concentrations of PhSiH3 (a) and nonꢀ1ꢀene (b) versus time in the hydrosilylation (Т = 20 0.5 °C, C6D6, Ccat = 0.0062 mol L–1
C0 = C0nonꢀ1ꢀene = 0.309 mol L–1).
,
PhSiH
3
4 + ln[C/C0]
3.0
4 + ln[C/C0]
a
b
3.0
2.5
2.0
1.5
1.0
0.5
2.5
2.0
1.5
1.0
0.5
2
4
6
8
10
12
14 t/h
2
4
6
8
10
12
14 t/h
Fig. 2. Parameter ln[C/C0] for phenylsilane (a) and nonꢀ1ꢀene (b) versus time in the hydrosilylation (T = 20 0.5 °C, C6D6,
Ccat = 0.0062 mol L–1, C0
C/mol L–1
= 0.309 mol L–1, C0nonꢀ1ꢀene = 0.3085 mol L–1).
PhSiH
3
4 + ln[C/C0]
a
b
2.5
2.0
1.5
1.0
0.5
0.25
0.20
0.15
0.10
0.05
10
20
30
40
50 t/h
10
20
30
40
50 t/h
Fig. 3. Concentration of nonꢀ1ꢀene (a) and parameter ln[C/C0] for nonꢀ1ꢀene (b) versus time in the hydrosilylation (T = 20 0.5 °C,
C6D6, Ccat = 0.0061 mol L–1, C0 = 1.1325 mol L–1, C0nonꢀ1ꢀene = 0.2265 mol L–1).
PhSiH
3

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Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
Lyubov et al.
C/mol L–1
0.25
C/mol L–1
0.25
1
2
3
0.20
0.15
0.10
0.05
0.20
0.15
0.10
0.05
20
40
60
80 t/h
50
100
150
200
250 t/h
Fig. 4. Concentration of PhSiH3 versus time in the presence of
a fiveꢀfold molar excess of nonꢀ1ꢀene (T = 20 0.5 °C, C6D6,
Fig. 5. Current concentrations of PhSiH3 (1), Ph(nꢀC9H19)SiH2
(2) and Ph(nꢀC9H19)2SiH (3) versus time in the hydrosilylation
Ccat = 0.0045 mol L–1, C0
= 0.2191 mol L–1, C0
=
(Т = 20 0.5 °C, C6D6, Ccat = 0.0045 mol L–1, C0
= 0.2191 mol L–1, C0nonꢀ1ꢀene = 1.1093 mol L–1).
=
PhSiH
3
PhSiH
nonꢀ1ꢀene
3
= 1.1093 mol L–1).
bond of the catalyst, whereas the metathesis reaction of
the Y—C σꢀbond upon the action of phenylsilane proꢀ
ceeds rapidly.
known fact indicating that the primary silanes are much
more reactive in the hydrosilylation reactions as compared
to the secondary.33
It should be noted that the first order in olefin and zero
order in silane were also observed in the case of hydrosilyꢀ
lation of octꢀ1ꢀene with PhMeSiH2 in the presence
of [(ButC5H4)2LnH]2 (Ln = Tb, Yb, Lu),20 whereas
the reaction of hexꢀ1ꢀene with PhMeSiH2 catalyzed by
a [MeC6H3N(Me2SiBut)]2YMe(THF)2 complex has the
first order in silane and zero in olefin.31 Addition of PhSiH3
to the double bond of 2ꢀphenylbutꢀ1ꢀene in the presence
of (R)ꢀMe2Si(C5Me4)[(–)ꢀmenthylCp]SmCH(SiMe3)2
has also the first order in silane and zero in olefin.15 The
facts indicated clearly demonstrate that, depending on the
structure of the olefin and silane, as well as on the nature
of the catalyst, different steps of the catalytic cycle can
determine the overall rate of the process.
During determination of the reaction order in phenylꢀ
silane in the presence of excess nonꢀ1ꢀene, it was
found that hydrosilylation does not stop at the step of
Ph(nꢀC9H19)SiH2 formation. The latter reacts with the
second molecule of nonꢀ1ꢀene, leading to the tertiary silane
Ph(nꢀC9H19)2SiH (Scheme 2). This is indicated by the
decrease in the integral intensity of the characteristic triꢀ
plet at δ 4.39 related to the protons SiH2, and by appearꢀ
ance of the signal at δ 4.32 in the 1H NMR spectrum of the
reaction mixture. The growing signal related to the SiH
group is a quintet due to the splitting of the proton on the
four hydrogen atoms of the methylene groups of two
nꢀnonyl substituents. From the curve of concentrations of
PhSiH3 and Ph(nꢀC9H19)SiH2 versus time (Fig. 5), it is
seen that initially all the primary phenylsilane is consumed
and only then the secondary silane Ph(nꢀC9H19)SiH2
would react. The picture observed correlates with the
Scheme 2
When the reaction of PhSiH3 with excess of nonꢀ1ꢀene
has been carried out in the presence of complex 1 on
a preparative scale, the tertiary silane Ph(nꢀC9H19)2SiH
was isolated in 91% yield.
This result is interesting by the fact that usually for the
lanthanideꢀcontaining catalytic systems, hydrosilylation
with participation of primary silanes is limited to the single
addition of one olefin molecule to the double bond, and
secondary silanes formed do not further react. The fact
described above is the first example of double addition of
alkenes to phenylsilane in the presence of the rareꢀearth
metal complexes, which leads to the formation of tertiary
silane.
In conclusion, we found that yttrium and lutetium bisꢀ
guanidinate hydride complexes are efficient and selective
catalysts for the hydrosilylation of nonꢀ1ꢀene with pheꢀ
nylsilane. The reactions proceed at room temperature
in quantitative yields and with exclusive formation of
antiꢀMarkovnikov addition product. Addition of PhSiH3
to the double bond of nonꢀ1ꢀene in the presence of

Lanthanide hydrides in hydrosilylation
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
1769
a {[(Me3Si)2NC(NPri)2]2Y(μꢀH)}2 complex has the first
order in olefin and the zero in phenylsilane. This is an
evidence that the rate determining stage of the process is
the insertion of nonꢀ1ꢀene into the Ln—H bond, whereas
metathesis of the Ln—C σꢀbond upon the action of phenylꢀ
silane is a fast process. In addition, we found the first
example of successive double alkylation of phenylsilane
with an olefin catalyzed by the rareꢀearth metal complex
with the formation of tertiary silane.
quenched and the product was isolated as described above. The
yield of Ph(nꢀC9H19)SiH2 was 0.77 g (94%).
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NCу)2]2Y(μꢀH)}2 (3). Phenylsilane (0.32 mL,
2.6 mmol) and nonꢀ1ꢀene (0.45 mL, 2.6 mmol) were added to
a solution of complex 3 (0.0869 g, 0.0528 mmol) in hexane
(5 mL). The reaction time was 12 h. The reaction mixture was
quenched and the product was isolated as described above. The
yield of Ph(nꢀC9H19)SiH2 was 0.57 g (94%).
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NCу)2]2Lu(μꢀH)}2 (4). Phenylsilane (0.34 mL,
2.7 mmol) and nonꢀ1ꢀene (0.47 mL, 2.7 mmol) were added to
a solution of complex 4 (0.0983 g, 0.0540 mmol) in hexane
(5 mL). The reaction time was 12 h. The reaction mixture was
quenched and the product was isolated as described above. The
yield of Ph(nꢀC9H19)SiH2 was 0.61 g (96%).
Experimental
All the manipulations on the synthesis and isolation of prodꢀ
ucts were performed in vacuo using standard Schlenk techꢀ
nique. Tetrahydrofuran after drying with potassium hydroxꢀ
ide was distilled over sodium benzophenone ketyl. Hexane
and benzene were dried by reflux and distillation over soꢀ
dium metal. Phenylsilane was dried with calcium hydride,
degassed and condensed into the reaction tube directly before
use. Nonꢀ1ꢀene, styrene, and N,N´ꢀdiisopropylcarbodiimide
were degassed in vacuo and used after drying over moleꢀ
cular sieves A4. Commercial reagent N,N´ꢀdicyclohexylcarboꢀ
diimide was used as purchased. Benzeneꢀd6 was dried with
metallic sodium, degassed, and condensed in vacuo; CDCl3 was
used as purchased. NMR spectra were recorded on a Bruker
DPX 200 spectrometer (200 (1H) and 50 MHz (13C)). Liquid
chromatography was performed on a KNAUER chromatograph
(a Separon SGXC 18 column, MeCN—H2O was an eluent).
The reaction progress was monitored on a Tsvet 530 gasꢀliquid
chromatograph.
Reaction of PhSiH3 with a fiveꢀfold molar excess
of nonꢀ1ꢀene on a preparative scale
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NPri)2]2Y(μꢀH)}2 (1). Phenylsilane (0.20 mL,
1.6 mmol) and nonꢀ1ꢀene (1.36 mL, 7.9 mmol) were added to
a solution of complex 1 (0.0418 g, 0.032 mmol) in hexane (5 mL).
The reaction mixture was stirred for 24 h. To stop the reaction,
1ꢀbromobutane (1 mL) was added to the reaction mixture. The
solution was filtered, volatile organic compounds were evapoꢀ
rated in vacuo at room temperature. A liquid residue of highꢀ
boiling products was distilled at reduced pressure (0.05 Torr,
180—210 °C) to yield Ph(nꢀC9H19)2SiH (0.34 g, 91%). Found (%):
C, 80.12; H, 12.51. C24H44Si. Calculated (%): C, 79.92;
H, 12.30. 1H NMR (CDCl3), δ: 0.93 (br.m, 10 H, CH3 + SiCH2);
1.31 (br.m, 28 H, CH2); 4.39 (quint, 1 H, SiH, 2JH,H = 3.3 Hz);
7.41—7.63 (m, 5 H, SiC6H5). 13C{1H} NMR (CDCl3), δ: 11.9
(SiCH2); 14.1 (CH3); 22.7, 24.5, 29.3, 29.4, 29.5, 31.9, 33.3
(CH2); 127.9, 129.1, 134.7, 136.2 (CAr). IR (KBr), ν/cm–1: 466,
701, 732, 822, 940, 1013, 1115, 1169, 1260, 1300, 1378, 1408,
1426, 1465, 1589, 1734, 1759, 1813, 1876, 1949, 2109, 3015,
3049, 3070.
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NPri)2]2Lu(μꢀH)}2 (2). Phenylsilane (0.11 mL,
0.9 mmol) and nonꢀ1ꢀene (0.77 mL, 4.5 mmol) were added to
a solution of complex 2 (0.0287 g, 0.019 mmol) in hexane (5 mL).
The reaction time was 24 h. The reaction mixture was quenched
and the product was isolated as described above. The yield of
Ph(nꢀC9H19)2SiH was 0.29 g (91%).
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NCу)2]2Y(μꢀH)}2 (3). Phenylsilane (0.32 mL,
2.6 mmol) and nonꢀ1ꢀene (2.28 mL, 13.2 mmol) were added to
a solution of complex 3 (0.0869 g, 0.053 mmol) in hexane (3 mL).
The reaction time was 24 h. The reaction mixture was quenched
and the product was isolated as described above. The yield of
Ph(nꢀC9H19)2SiH was 0.32 g (93%).
Reaction of equimolar amounts of nonꢀ1ꢀene
and PhSiH3 on a preparative scale
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NPri)2]2Y(μꢀH)}2 (1). Phenylsilane (0.20 mL,
1.6 mmol) and nonꢀ1ꢀene (0.28 mL, 1.6 mmol) were added to
a solution of complex 1 (0.0418 g, 0.0316 mmol) in hexane
(5 mL). The reaction mixture was stirred for 12 h at room
temperature. To stop the reaction, 1ꢀbromobutane (1 mL)
was added to the reaction mixture. The solution was filtered,
volatile organic compounds were evaporated in vacuo at room
temperature. A liquid residue of the highꢀboiling products
was distilled at reduced pressure (0.05 Torr, 180—210 °C) to
yield Ph(nꢀC9H19)SiH2 (0.34 g, 91%). Found (%): C, 76.34;
H, 11.23. C15H26Si. Calculated (%): C, 76.84; H, 11.18.
1H NMR (CDCl3), δ: 0.93 (br.m, 5 H, CH3 + SiCH2); 1.31
2
(br.m, 14 H, CH2); 4.39 (t, 2 H, SiH2, JH,H = 3.6 Hz);
7.41—7.63 (m, 5 H, SiC6H5). 13C{1H} NMR (CDCl3), δ: 10.1
(SiCH2, C(8)); 14.2 (CH3, C(16)); 22.8, 25.2, 29.3, 29.4,
29.6, 31.9, 32.9 (CH2); 127.9, 129.5, 135.3, 132.9 (CAr). IR
(KBr), ν/cm–1: 454, 505, 563, 662, 699, 635, 840, 938, 1115,
1169, 1252, 1299, 1378, 1589, 1638, 1813, 1879, 1950, 2130,
3015, 3051, 3069.
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NCу)2]2Lu(μꢀH)}2 (4). Phenylsilane (0.09 mL,
0.7 mmol) and nonꢀ1ꢀene (0.6 mL, 3.5 mmol) were added to
a solution of complex 4 (0.0253 g, 0.014 mmol) in hexane (5 mL).
The reaction time was 24 h. The reaction mixture was quenched
and the product was isolated as described above. The yield of
Ph(nꢀC9H19)2SiH was 0.24 g (94%).
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
{[(Me3Si)2NC(NPri)2]2Lu(μꢀH)}2 (2). Phenylsilane (0.44 mL,
3.5 mmol) and nonꢀ1ꢀene (0.62 mL, 3.5 mmol) were added to
a solution of complex 2 (0.1034 g, 0.0690 mmol) in hexane
(5 mL). The reaction time was 12 h. The reaction mixture was

1770
Russ.Chem.Bull., Int.Ed., Vol. 59, No. 9, September, 2010
Lyubov et al.
Hydrosilylation of nonꢀ1ꢀene with phenylsilane
in the presence of complex 1 (NMRꢀmonitoring)
16. G. A. Molander, W. H. Retsch, J. Am. Chem. Soc., 1997,
119, 8817.
17. G. A. Molander, E. D. Dowdy, B. C. Noll, Organometallics,
1997, 17, 3754.
18. K. Takaki, K. Sonoda, T. Kousaka, G. Koshoji, T. Shishido,
K. Takehira, Tetrahedron Lett., 2001, 42, 9211.
19. Z. Hou, Y. Zhang, O. Tardif, Y. Wakatsuki, J. Am. Chem.
Soc., 2001, 123, 9216.
20. A. Z. Voskoboynikov, A. K. Shestakova, I. P. Beletskaya,
Organometallics, 2001, 20, 2794.
21. A. A. Trifonov, T. P. Spaniol, J. Okuda, Organometallics,
2001, 20, 4869.
22. O. Tardif, M. Nishiura, Z. Hou, Tetrahedron, 2003, 59,
10525.
23. Y. Horino, T. Livinghouse, Organometallics, 2004, 23, 12.
24. D. Robert, A. A. Trifonov, P. Voth, J. Okuda, J. Organomet.
Chem., 2006, 691, 4393.
25. A. A. Trifonov, T. P. Spaniol, J. Okuda, J. Chem. Soc., Dalꢀ
ton Trans., 2004, 2245.
26. G. A. Molander, J. A. Antoinette, C. Romeo, Chem. Rev.,
2002, 102, 2161.
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 with the ratio of
reagents 1 : 1. Phenylsilane (0.045 mL, 0.36 mmol) and nonꢀ1ꢀ
ene (0.061 mL, 0.36 mmol) were added to a weighted amount of
complex 1 (0.009 g, 0.0068 mmol, 2 mol.%) dissolved in benꢀ
zeneꢀd6 (1 mL). The reaction was monitored by NMR for 3 days.
Hydrosilylation of nonꢀ1ꢀene with PhSiH3 in the presence of
a fiveꢀfold excess of nonꢀ1ꢀene. Phenylsilane (0.06 mL, 0.5 mmol)
and nonꢀ1ꢀene (0.45 mL, 2.6 mmol) were added to a weighted
amount of complex 1 (0.0138 g, 0.0104 mmol, 2.1 mol.%) disꢀ
solved in benzeneꢀd6 (1 mL). The reaction was monitored by
NMR for 3 days.
Hydrosilylation of nonꢀ1ꢀene with the excess of phenylsilane.
Phenylsilane (0.24 mL, 1.9 mmol) and nonꢀ1ꢀene (0.066 mL,
0.39 mmol) were added to a weighted amount of complex 1
(0.0102 g, 0.0077 mmol, 1.8 mol.%) dissolved in benzeneꢀd6
(1 mL). The reaction was monitored by NMR for 3 days.
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Received March 24, 2010;
in revised form June 2, 2010