TY - JOUR
T1 - Stoichiometric hydrosilylation of nitriles with hydrido(hydrosilylene) tungsten complexes
T2 - Formation of W-Si-N three-membered ring complexes and their unique thermal behaviors
AU - Watanabe, Takahito
AU - Hashimoto, Hisako
AU - Tobita, Hiromi
PY - 2006/2/22
Y1 - 2006/2/22
N2 -
Reactions of hydrido(hydrosilylene)tungsten complexes, Cp′(CO)
2
(H)W=Si(H)[C(SiMe
3
)
3
], with nitriles (MeCN,
t
BuCN) at 60 °C gave hydrosilylation products, Cp′(CO)
2
W[κ
2
(N,Si)-Si(H)(N=CHR′){C(SiMe
3
)
3
}] (R′ = Me,
t
Bu), with a novel W-Si-N three-membered ring structure. The product of the hydrosilylation of
t
BuCN underwent reversible rearrangement at 70 °C to a silylene complex, Cp′(CO)
2
(H)W=Si(N=CH
t
Bu)[C(SiMe
3
)
3
], which was a major component in equilibrium. A reaction mechanism for the hydrosilylation involving coordination of nitriles to the silylene ligand and subsequent migration of the hydrido ligand to the nitrile carbon was proposed.
AB -
Reactions of hydrido(hydrosilylene)tungsten complexes, Cp′(CO)
2
(H)W=Si(H)[C(SiMe
3
)
3
], with nitriles (MeCN,
t
BuCN) at 60 °C gave hydrosilylation products, Cp′(CO)
2
W[κ
2
(N,Si)-Si(H)(N=CHR′){C(SiMe
3
)
3
}] (R′ = Me,
t
Bu), with a novel W-Si-N three-membered ring structure. The product of the hydrosilylation of
t
BuCN underwent reversible rearrangement at 70 °C to a silylene complex, Cp′(CO)
2
(H)W=Si(N=CH
t
Bu)[C(SiMe
3
)
3
], which was a major component in equilibrium. A reaction mechanism for the hydrosilylation involving coordination of nitriles to the silylene ligand and subsequent migration of the hydrido ligand to the nitrile carbon was proposed.
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U2 - 10.1021/ja056715p
DO - 10.1021/ja056715p
M3 - Article
C2 - 16478147
AN - SCOPUS:33644515286
VL - 128
SP - 2176
EP - 2177
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 7
ER -