Bis(acetylacetonato)Ni(II)/NaBHEt3-catalyzed hydrosilylation of 1,3-dienes, alkenes and alkynes

Article abstract of DOI:10.1016/j.jorganchem.2016.02.025

The utility of commercially available Ni(II) salts, Ni(acac)₂ (acac = acetylacetonato) (1a) and its derivatives bis(hexafluoroacetylacetonato)nickel(II) (1b) and bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II) (1c) as versatile hydrosilylation catalyst precursors is described. Complexes 1a-c catalyze 1,4-selective hydrosilylation of 1,3-dienes in the presence of NaBHEt₃ at ambient temperature. The reactions exhibit good regioselectivity to give the branched isomers as major products. The catalytic system also catalyzes hydrosilylation of alkenes including industriary important siloxy-, amino-, and epoxy-substituted ones as well as both terminal and internal alkynes.

Full text of DOI:10.1016/j.jorganchem.2016.02.025

Accepted Manuscript
Bis(acetylacetonato)Ni(II)/NaBHEt -catalyzed hydrosilylation of 1,3-dienes, alkenes
3
and alkynes
Venu Srinivas, Yumiko Nakajima, Wataru Ando, Kazuhiko Sato, Shigeru Shimada
PII:
S0022-328X(16)30058-4
10.1016/j.jorganchem.2016.02.025
JOM 19409
DOI:
Reference:
To appear in: Journal of Organometallic Chemistry
Received Date: 16 December 2015
Revised Date: 9 February 2016
Accepted Date: 18 February 2016
Please cite this article as: V. Srinivas, Y. Nakajima, W. Ando, K. Sato, S. Shimada,
Bis(acetylacetonato)Ni(II)/NaBHEt -catalyzed hydrosilylation of 1,3-dienes, alkenes and alkynes,
3
Journal of Organometallic Chemistry (2016), doi: 10.1016/j.jorganchem.2016.02.025.
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ACCEPTED MANUSCRIPT
Graphical abstract

ACCEPTED MANUSCRIPT
Bis(acetylacetonato)Ni(II)/NaBHEt3-catalyzed hydrosilylation of 1,3-dienes,
alkenes and alkynes
Venu Srinivas,a Yumiko Nakajima,*a Wataru Ando,a Kazuhiko Sato,a Shigeru
Shimada*a
aNational Institute of Advanced Industrial Science and Technology (AIST), Tsukuba
Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
E-mail address: yumiko-nakajima@aist.go.jp (Y. Nakajima), s-shimada@aist.go.jp (S.
Shimada).
Abstract The utility of commercially available Ni(II) salts, Ni(acac)2 (acac =
acetylacetonato) (1a) and its derivatives bis(hexafluoroacetylacetonato)nickel(II) (1b)
and
bis(2,2,6,6-tetramethyl-3,5-heptanedionato)nickel(II)
(1c)
as
versatile
hydrosilylation catalyst precursors is described. Complexes 1a-c catalyze 1,4-
selective hydrosilylation of 1,3-dienes in the presence of NaBHEt3 at ambient
temperature. The reactions exhibit good regioselectivity to give the branched isomers
as major products. The catalytic system also catalyzes hydrosilylation of alkenes
including industriary important siloxy-, amino-, and epoxy-substituted ones as well as
both terminal and internal alkynes.
Keywords
Hydrosilylation, Nickel, Olefin
1. Introduction
Hydrosilylation reaction of carbon-carbon multiple bonds is one of the most important
processes for the production of orgaosilicon compounds and for the curing of
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organosilicon materials [1]. For these reactions, precious metal complexes containing
Pt, Rh, Ru etc., are widely used as catalysts. On the other hand, due to the low
abundance and high cost of these metals [2], there is an emerging demand to develop
inexpensive and environmentally benign earth-abundant metal catalysts. So far,
several 3d metal catalysts containing Fe [3], Co [4] and Ni [5] have been revealed to
be good candidates for non-precious metal surrogates. However, 3d metal complexes
often exhibit diverse reactivity, and thus many side reactions simultaneously proceed
during the catalytic reactions, leading to the formation of a complicated reaction
mixture. In recent years, well-defined Fe catalysts with good selectivity have been
developed. One notable example was reported by Chirik et al. using iron complexes
bearing bis(imono)pyridine (PDI = 2,6-(2,6-R2C6H3N=CMe)2C5H3N), [Fe(PDI)(N2)2]
i
(R = Pr) and [(PDI)Fe(N2)]2(µ2-N2) (R = Et, Me), which exhibit higher reaction
selectivity than platinum-based industrial catalysts [3c]. Another example is the
bis(iminopyridine) Fe complex system, which demonstrated the first example of
regio- and stereoselective hydrosilylation of 1,3-dienes [3a]. These examples
successfully demonstrate the high capability of 3d metal complexes as a
hydrosilylation catalyst although the systems still have room to be improved, such as
high instability and complicated preparation method of the catalysts, etc.
The use of the commercially available Ni(II) salts, Ni(acac)2 (acac = acetylacetonato)
(1a) as a hydrosilylation catalyst has been reported in 1991 under rather harsh
reaction conditions with low reaction selectivity [5d-f]. It is also reported that 1a in
conjunction with a proper reducing agent such as alkyl aluminum reagents AlR3 [R3 =
Et3, Et2(OEt)], LiAlH4, and BuMgBr effectively catalyzes 1,4-selective
hydrosilylation of 1,3-dienes at ambient temperature, while the system is not
applicable to normal α-alkene hydrosilylation reactions [5b,c]. Since simple and air
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stable 1a is a promising catalyst precursor, it is of great interest to further investigate
the capability of 1a as a hydrosilylation catalyst. In this study, we found that 1a and
its derivatives bis(hexafluoroacetylacetonato)nickel(II) (1b) and bis(2,2,6,6-
tetramethyl-3,5-heptandiono)nickel(II) (1c) (Figure 1), serve as
a
good
hydrosilylation catalyst precursor in the presence of NaBHEt3.
R
R
O
O
O
O
Ni
R
R
R = Me (1a), CF3 (1b), tBu (1c)
Figure 1. Structures of 1a-c
Different from the previous systems, our system 1/NaBHEt3 catalyzes
hydrosilylation not only of 1,3-dienes but also of α-alkenes at room temperature with
a good selectivity. It was also revealed that the system catalyzed hydrosilylation of
alkynes, furnishing monohydrosilylated products in moderate yields.
2. Results and discussion
Hydrosilylation of 1,3-dienes. It was revealed that the 1a/NaBHEt3 system exhibits
similar catalytic performance as the previous system 1a/AlEt3 in hydrosilylation
reactions of various 1,3-dines with (EtO)3SiH. The reaction was performed at room
temperature in THF using each 1.0 mmol of substrates and 0.5 mol% of 1a/NaBHEt3.
Hydrosilylation of cyclohexadiene proceeded in a 1,4-fashion to form 3-
triethoxysilylcyclohexene in 75% yield (Table 1, entry 1). Formation of (EtO)4Si
(4%) was also observed, indicating the occurrence of substituent redistribution of
(EtO)3SiH as a side reaction.[6] Isoprene hydrosilylation also proceeded in a 1,4-
fashion, resulting in the formation of the corresponding hydrosilylated products as a
mixture of two isomers, branched isomer, (Z)-2-methyl-1-triethoxysilyl-2-butene, and
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linear isomer, 3-methyl-1-triethoxysilyl-2-butene, within 2 h in 79% total yield (Table
1, entry 2). In this reaction, the branched isomer was obtained predominantly
(branched:linear = 79/21), accompanied by the slight formation of (EtO)4Si (2%) and
(EtO)3SiOSi(OEt)3 (4%). In this system, the order of substrate addition is critical for
the reaction selectivity. When 1a and NaBHEt3 were initially mixed and then
(EtO)3SiH and isoprene were successively added, substituent redistribution of the
silane perferably proceeded to form a mixture of (EtO)4Si (12%), (EtO)3SiOSi(OEt)3
(6%), etc, as well as less amount of hydrosilylated products (61% total yield,
branched:linear = 72/28). Superior results were obtained by the addition of silane and
isoprene to the THF solution of 1a and subsequent addition of NaBHEt3. Therefore,
all the reactions in Table 1 were performed following the latter procedure.
Myrecene was also hydrosilylated with (EtO)3SiH in 1 h, resulting in the formation of
1,4-adducts in 85% yields (branched:linear = 90/10) (Table 1, entry 3). In this
reaction, various tertiary and secondary hydrosilanes were examined. The reactions
proceeded under the same conditions, leading to the formation of 1,4-hydrosilylated
products with good branched selectivity (Table 1, entries 3,4).
Different from above reactions, hydrosilylation of 1,3-pentadiene resulted in the
formation of the linear isomer as a major product (93% total yield, branched:linear =
15/85) (Table 1, entry 5). Such a changeable regioselectivity was also reported in the
1,4-selective hydrosilylation of 1,3-dienes catalyzed by the previous 1a/AlEt3 system
[5b]
Next, catalytic activities of 1b and 1c were similarly surveyed using isoprene and
(EtO)3SiH as standard substrates (Table 1, entry 2). The reactions also proceeded in a
1,4-fashion to predominantly give the branched product. Complex 1b with electron
withdrowing CF3 groups exhibited slightly higher catalytic activity than 1a to furnish
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the hydrosilylated products mixture in 88% total yield within 1 h. On the other hand,
the activity of 1c with bulky tBu groups was less; i.e. the reaction took 4 h to give the
1,4-hydrosilylated products in 76% total yield (Table 1, entry 2).
Table 1
1a-1c/NaBHEt3-catalyzed hydrosilylation of 1,3-dienesa
Poduct yieldsb
(branched : linear)
Entry Cat
R3SiH + 1,3-diene
(EtO)3SiH
+
1
2
1a
75% c
(EtO)3SiH
+
1a (2 h): 79% (79 : 21)c
1b (1 h): 88% (81 : 19)c
1c (4 h): 76% (78 : 22)c
1a-c
R3SiH
R3 = (EtO)3 (1 h): 85% (90 : 10) c
R3 = (EtO)2Me (2 h): 81% (95:5)
R3 = Et3 (3 h): 81% (95:5)
3
1a
+
R3 = (Me3SiO)2Me (10 h): 74% (90:10)
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R2SiH2
4
5
1a
1a
R2 = Ph2 (8 h); 82% (78:22)d
R2 = Et2 (2 h): 65% (98:2)
+
(EtO)3SiH
+
2 h; 93% (15:85)
aReaction conditions: catalyst/NaBHEt3 (0.005/0.005 mmol), alkene (1.0 mmol), silane (1.0
mmol), in THF (5 mL) at room temperature; bIsolated yield; c(EtO)4Si (2-4%) was isolated as a
byproduct; dPh3SiH (6%) was isolated as a byproduct.
Hydrosilylation of alkenes. It was reported that selective hydrosilylation of α-
alkenes is not successful by using 1a with or without any additives as a catalyst in the
previous attempts.[5b, 5f] On the other hand, it was found that 1a and 1b catalyzed
alkene hydrosilylation reactions in the presence of NaBHEt3 although the reaction
proceeded at slower rate compared with the 1,3-diene hydrosilylation reactions.
Hydrosilylation of 1-octene took place at 50 °C in the presence of 1a (0.5 mol%) and
NaBHEt3 (0.5 mol%) to selectively form anti-Markovnikov product (nOct)(EtO)3Si in
85% isolated yield (Table 2, entry 1). Small amounts of (EtO)4Si (5%) and internal
alkenes (< 5%) were also formed. Styrene and norbornene were also hydrosilylated at
higher catalyst loading (1.0 mol%) of 1b, resulting in the formation of the
corresponding hydrosilylated products in moderate yields (Table 2, entries 2, 3). It is
interesting that, unlike a previously reported 1a-catalyzed reaction of styrene with
(EtO)3SiH,
which
selectively
formed
dehydrosilylated
product,
(EtO)3SiCH=CHPh[5g], the present catalyst system gave the hydrosilylated product
selectively.
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The system was also utilized for hydrosilylation of industrially important alkenes
with various functional groups, such as epoxy[3d,5k,7,9], amino[5k,7,8] and
siloxy[7] groups (entries 4-6). It is to be noted that 1,2-epoxy-4-vinylcyclohexane,
which often undergoes ring-opening polymerization in the hydrosilylation reaction
catalyzed by Pt catalysts [10], was selectively hydrosilylated with Ph2SiH2 to give
1,2-epoxy-4-(2-diphenylsilylethyl)cyclohexane in 83% yield.
Table 2
1a-1b/NaBHEt3-catalyzed hydrosilylation of alkenesa
1
(x mol%)
NaBEt3H (x mol%)
R3Si
R'
R'
R3SiH +
THF, time, T °C
Cat
(mol%)
time (h)/
T (°C)
Product
entry
1
R3SiH
Yield (%)b
85%c
1a (0.5) (EtO)3SiH
1b (1.0) (EtO)3SiH
10/50
nC6H13
42%d
52%d
2
3
72/50
96/50
Ph
1b (1.0) (EtO)3SiH
Ph2HSi
4
1a (0.5)
Ph2SiH2
4/ RTe
O
83%f
88% f
O
Ph2HSi
NMe2
1/ RTe
14/RTe
NMe2
5
6
1a (0.5)
1a (0.5)
Ph2SiH2
Ph2SiH2
Ph2HSi
SiMe(OMe)2
SiMe(OMe)2
72% f
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aReaction conditions: catalyst/NaBHEt3 (0.005/0.005 mmol), alkene (1.0 mmol), silane (1.0
b
c
d
mmol), in THF (5 mL) ; Isolated yield; (EtO)4Si (5%) was isolated; (EtO)4Si (10%) and
(EtO)3OSi(OEt)3 (5%) were also isolated. Unreacted styrene or 2-norbornene were recovered;
eRoom Temperature; Ph3SiH (2-3%) was also isolated
f
2.1 Alkyne hydrosilylation
The catalytic activity towards alkyne hydrosilylation was also surveyed. The results
are summarized in Table 3. The 1a/NaBHEt3 system exhibits a similar reactivity
towards a terminal alkyne hydrosilylation reaction as 1a/AlEt3, which produces 1,3-
butadienylsilane derivatives via successive alkyne coupling and hydrosilylation [5b].
Thus, the reaction of 1-pentyne with (EtO)3SiH proceeded at room temperature to
form CH2=C(nPr)C(nPr)=CH[Si(OEt)3] in 20% yield in the presence of 1a/NaBHEt3
(1 mol% each) (Table 3, entry 1). On the other hand, our catalyst system proved to be
effective for the hydrosilylation of internal alkynes, which did not proceed with the
previous 1a/AlEt3 system [5b]. Thus, hydrosilylation of diphenylacetylene with
(EtO)3SiH proceeded at room temperature in the presence of 1a (1.0 mol%) and
NaBHEt3 (1.0 mol%) to give monohydrosilylated product ((E)-1,2-
diphenylvinyl)triethoxysilane (63%) (entry 2). Analogously, dihydrosilanes, Ph2SiH2
and Et2SiH2, were also utilized in this reaction to form the corresponding
monohydrosilylated products in 58% and 64% yields, respectively (entries 3,4). The
reaction of an unsymmetrical alkyne, 1-phenyl-1-propyne, with (EtO)3SiH also
proceeded to give a mixture of (E)-triethoxy(1-phenylprop-1-en-2-yl)silane and (E)-
triethoxy(1-phenylprop-1-en-1-yl)silane (47%) in 7:3 ratio (entry 5). In this reaction,
formation of [2+2+2] cycloadduct, 2',4',6'-trimethyl-5'-phenyl-1,1':3',1''-terphenyl,
was also observed in 8% yield.
The difference of the catalytic activity between our 1a/NaBHEt3 and previous
1a/AlEt3 systems would suggest the presence of different catalytically active species.
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In the previous systems, Ni(0) is proposed as an active species [5b]. In contrast, we
confirmed that Ni(cod)2 (cod = cyclooctadiene) did not catalyze the hydrosilylation
reaction of diphenylacetylene with (EtO)3SiH. One possible reaction pathway for
1a/NaBHEt3 system is the mechanism initiated by the formation of a nickel hydride
species. However, preliminary experiments could not confirm the formation of the
active hydride species during the reaction [11]. Based on the experimental results that
other hydride reagents such as LiAlH4 and NaBH4 could not be utilized in our system,
it is likely that not a nickel(II)hydride but a nickel(II) complex adducted with a
triethylborohydride anion through B–H σ-coordination plays a key role in the
catalytic cycle. The attempts to elucidate the reaction mechanism are not successful at
this moment and further studies will be performed.
Table 3
1a/NaBHEt3-catalyzed hydrosilylation of alkynesa
t
Product
Entry
1
R3SiH
Alkyne
(h)
Yield (%)b
(EtO)3SiH
14
36
20%c
63%d
2
(EtO)3SiH
Ph
Ph
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3
4
5
Ph2SiH2
Et2SiH2
42
24
36
Ph
Ph
Ph
Ph
Ph
58%e
64%f
CH3
(EtO)3SiH
47% (7:3) g,h
aReaction conditions: catalyst/NaBHEt3 (0.01 mmol), alkyne (1.0 mmol), silane (1.0
b
c
mmol), in THF (5 mL); Isolated yield; (EtO)4Si (8%) and (EtO)3SiOSi(OEt)3 (2%)
d
were also isolated; (EtO)4Si (11%) and (EtO)3SiOSi(OEt)3 (6%) were isolated;
f
ePh3SiH (10%) was also isolated; Unreacted Et2SiH2 (ca. 20%) was recovered;
g(EtO)4Si (8%) and (EtO)3SiOSi(OEt)3 (7%) were also isolated; h[2+2+2] cycloadduct
[2',4',6'-trimethyl-5'-phenyl-1,1':3',1''-terphenyl] of 1-phenyl-1-propyne was also
isolated (8%).
Conclusion
In conclusion, hydrosilylation reaction was efficiently accomplished under
mild reaction conditions by using the commercially available nickel(II) salts 1a-c
combined with NaBHEt3 as a co-catalyst. The hydrosilylation of 1,3-dienes proceeded
with good 1,4-regioselectivity. The catalyst system is also applicable to alkenes with
various substituents and both terminal and internal alkynes to selectively afford the
corresponding hydrosilylated products in good to excellent yields. These studies
revealed that our 1a-c/NaBHEt3 systems exhibit a wider applicability in comparison
with the previous 1a-catalyzed systems especially in alkene and alkyne
hydrosilylation reactions.
Although significant progress has been recently made in the development of
3d metal hydrosilylation catalyst systems, most cases still suffer from several
problems, such as low selectivity, limited substrates scope, difficulty in handling due
to the low stability of the catalysts, etc. Thus, this study, which demonstrated the
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ACCEPTED MANUSCRIPT
utility of commercially available and cheap Ni(II) salts 1a-c as a versatile
hydrosilylation catalyst precursor, would expand the scope of 3d metal species in this
field. For the further improvement of the catalytic systems, precise design of the
system based on understanding of the mechanism is indispensable. Further detailed
study including mechanistic investigations is currently underway, and the results will
be reported in due course
3. Experimental
General considerations.
Unless otherwise noted, all manipulations were performed under a nitrogen
atmosphere using Schlenk techniques or a glove box. Toluene, benzene, hexane,
CH2Cl2 and THF were purified by a solvent purification system (MBraun SPS-
800/Glass Contour Ultimate Solvent System). Other solvents (benzene-d6, toluene-d8,
and THF-d8) were dried over sodium benzophenone ketyl and distilled. All reagents
were purchased from commercial suppliers and used without further purification
1
13
29
13
unless otherwise noted. H, C{1H} and Si{1H} NMR spectra (1H, 600 MHz; C,
150 MHz; 29Si, 119 MHz) were recorded using a Bruker AVANCE 600 spectrometer.
Chemical shifts are reported in
δ (ppm) and are referenced to the residual solvent
1
13
29
signals for H and to tetramethylsilane (0.0 ppm) for C and Si. GLC analysis was
performed on a Shimadzu GC-14B instrument (FID; CBP-1, 25 m × 0.25 mm).
Elemental analyses were carried out on a Thermo Scientific FLASH2000 CHNS
analyzer.
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Catalytic hydrosilylations. A typical procedure (Table 2, entry 1) is as follows. To a
stirred solution of Ni(acac)2 (1a) (1.3 mg, 0.005 mmol) in THF (5 mL) was added 1-
octene (112 mg, 1.0 mmol) and (EtO)3SiH (164 mg, 1.0 mmol) at room temperature.
After the mixture was stirred for 1 min, NaBHEt3 (1.0 M in THF, 5 µL, 0.005 mmol)
o
was added and the resulting mixture was heated at 50 C. The solution was stirred at
the same temperature, and the progress of the reaction was monitored by GLC. After
completion of the reaction, mesitylene (60 mg, 0.50 mmol) was added as an internal
standard to the reaction mixture. The GLC analysis of the resulting solution revealed
the formation of (EtO)3(nOct)Si (0.90 mmol, 90%) and (EtO)4Si (0.05 mmol, 5%).
The solution was concentrated under vacuum, and the residue was purified by gel
permeation chromatography (GPC) using toluene as an eluent to give (EtO)3(nOct)Si
1
(234 mg, 0.85 mmol, 85%). The H, 13C{1H} and 29Si{1H} NMR spectra of the
isolated compound are consistent with the reported data. A similar procedure was
employed for the hydrosilylation using other silanes and 1,3-diene/alkenes/alkynes.
These reactions were carried out at room temperature except for the reactions, Table 2,
entries 2-3. The 1H/13C NMR spectroscopic data for the new compounds are given in
the supplementary data.
Following the hydrosilylation reaction of 1-octene with (EtO)3SiH catalyzed by
1a/NaBHEt3. To an NMR tube equipped with a Teflon valve were added Ni(acac)2
(13.0 mg, 0.05 mmol), 1-octene (11.3 mg, 0.1 mmol), (EtO)3SiH (16.0 mg, 0.1 mmol),
and THF-d8 (0.5 mL). After the addition of NaBHEt3 (1.0 M in THF, 50 µL, 0.05
1
mmol) to this solution at room temperature, the reaction was followed by H NMR.
After 2 h, the reaction did not proceed and only the signals assignable to the starting
1
materials [1-octene and (EtO)3SiH] were detected by H NMR. The reaction was
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ACCEPTED MANUSCRIPT
further followed at 50 °C for 14 h, and formation of (EtO)3(nOct)Si (54%) as well as
(EtO)4Si (8%) and (EtO)3SiOSi(OEt)3 (7%) was observed. During the reaction, no
hydride signals were detected in the high field region (δ 0 – –30 ppm).
Attempted hydrosilylation of isoprene with (EtO)3SiH catalyzed by [Ni(η-4-
cycloocte-1-yl)(CF3C(O)CHCOCF3)]. An NMR tube equipped with a Teflon valve
was charged with a THF-d8 solution (0.5 mL) containing [Ni(η-4-cycloocte-1-
yl)(CF3C(O)CHCOCF3)] (19 mg, 0.05 mmol), isoprene (1.0 mmol), and (EtO)3SiH
1
(164 mg, 1.0 mmol). No significant changes were detected by H NMR at room
temperature for 24 h. However, formation of a small amount of the corresponding
1
o
hydrosilylated product (5%) was confirmed by H NMR at 50 C after 24 h. In the
reaction solution, insoluble black precipitates were also formed.
Acknowledgments
This work was supported by the "Development of Innovative Catalytic Processes for
Organosilicon Functional Materials" project (PL: K.S.) from the New Energy and
Industrial Technology Development Organization (NEDO).
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[1]
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(2015) 20603.
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[4]
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For Ni-catalyzed alkene hydrosilylation see: (a) Y. Kiso, M. Kumada, K.
Tamao, M. Umeno, J. Organomet. Chem. 50 (1973) 297; (b) M. F. Lappert, T.
A. Nile, S. Takahashi J. Organomet. Chem. 72 (1974) 425; (c) A. J. Cornish,
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M. F. Lappert, T. A. Nile, J. Organomet. Chem. 132 (1977) 133; (d) B.
Marciniec, H. Maciejewski, J, Mirecki, J. Organomet. Chem. 418 (1991) 61;
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4759; (i) L. B. Junquera, M. C. Puerta, P. Valerga, Organometallics 31 (2012)
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Clerc, X. Hu, Angew. Chem. Int. Ed. 54 (2015) 14523.
[6]
It was confirmed that the substituent redistribution of (EtO)3SiH proceeded in
the presence of 1.0 mol% of 1a/NaBHEt3 to give (EtO)4Si (35%), and
(EtO)3SiOSi(OEt)3 (18%) in 8 h.
[7]
[8]
J. W. White in Progress in Organosilicon Chemistry (B. Marciniec, J.
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I. E. Markó, S. Stérin, O. Buisine, G. Berthon, G. Michaud, B. Tinant, J.-P.
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[10] J. V. Crivello, M. Fan, J. Polym. Sci, Part A: Polym. Chem. 29 (1991) 1853.
[11] Attempts to detect a nickel hydride species by following the reaction using 1H
NMR spectrum were not successful. It was also confirmed that [Ni(η-4-
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cycloocte-1-yl)(CF3C(O)CHCOCF3)], which was reported to be converted to a
nickel hydride complex after the elimination of cyclooctadiene [12], did not
catalyze the hydrosilylation of 1-octene with (EtO)3SiH at room temperature.
[12] (a) W. Keim, B. Hoffmann, R. Lodewick, M. Peuckert, G. Schmitt, J.
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