Three- and five-membered W/C/N metallacycles formed by incorporation of acetonitrile molecules into silyltungsten intermediates

Eiji Suzuki; Takashi Komuro; Masaaki Okazaki; Hiromi Tobita

doi:10.1021/om700514d

Three- and five-membered W/C/N metallacycles formed by incorporation of acetonitrile molecules into silyltungsten intermediates

Eiji Suzuki, Takashi Komuro, Masaaki Okazaki, Hiromi Tobita

Institute for Excellence in Higher Education (IEHE) (organization affiliation only)

Research output: Contribution to journal › Article › peer-review

18 Citations (Scopus)

Abstract

Treatment of Cp*(CO)₂W(NCMe)Me (Cp* = η⁵-C₅Me₅) with HSiR₃ (R = Et, p-Tol) afforded N-silylated η²-iminoacyl tungsten complexes Cp*(CO)₂W{κ²(C,N)-C(Me)= N(SiR₃)} (1a, R = Et; 1b, R = p-Tol). Analogous reactions in the presence of excess acetonitrile for a prolonged reaction time led to the formation of five-membered metallacycles Cp*(CO)₂W{κ²(C,N)-C(Me)=N-C(Me) =N(H)} (2) and Cp*(CO)₂W{κ²(C,N)-C(CH ₂SiR₃)=N-C(Me)=N(H)} (3, R = p-Tol) through a C-N coupling of nitrile molecules and migration of a silyl group.

Original language	English
Pages (from-to)	4379-4382
Number of pages	4
Journal	Organometallics
Volume	26
Issue number	18
DOIs	https://doi.org/10.1021/om700514d
Publication status	Published - 2007 Aug 27

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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@article{0d5a0e75cafd4420a196a92d61c76b74,

title = "Three- and five-membered W/C/N metallacycles formed by incorporation of acetonitrile molecules into silyltungsten intermediates",

abstract = "Treatment of Cp*(CO)2W(NCMe)Me (Cp* = η5-C5Me5) with HSiR3 (R = Et, p-Tol) afforded N-silylated η2-iminoacyl tungsten complexes Cp*(CO)2W{κ2(C,N)-C(Me)= N(SiR3)} (1a, R = Et; 1b, R = p-Tol). Analogous reactions in the presence of excess acetonitrile for a prolonged reaction time led to the formation of five-membered metallacycles Cp*(CO)2W{κ2(C,N)-C(Me)=N-C(Me) =N(H)} (2) and Cp*(CO)2W{κ2(C,N)-C(CH 2SiR3)=N-C(Me)=N(H)} (3, R = p-Tol) through a C-N coupling of nitrile molecules and migration of a silyl group.",

author = "Eiji Suzuki and Takashi Komuro and Masaaki Okazaki and Hiromi Tobita",

year = "2007",

month = aug,

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doi = "10.1021/om700514d",

language = "English",

volume = "26",

pages = "4379--4382",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Three- and five-membered W/C/N metallacycles formed by incorporation of acetonitrile molecules into silyltungsten intermediates

AU - Suzuki, Eiji

AU - Komuro, Takashi

AU - Okazaki, Masaaki

AU - Tobita, Hiromi

PY - 2007/8/27

Y1 - 2007/8/27

N2 - Treatment of Cp*(CO)2W(NCMe)Me (Cp* = η5-C5Me5) with HSiR3 (R = Et, p-Tol) afforded N-silylated η2-iminoacyl tungsten complexes Cp*(CO)2W{κ2(C,N)-C(Me)= N(SiR3)} (1a, R = Et; 1b, R = p-Tol). Analogous reactions in the presence of excess acetonitrile for a prolonged reaction time led to the formation of five-membered metallacycles Cp*(CO)2W{κ2(C,N)-C(Me)=N-C(Me) =N(H)} (2) and Cp*(CO)2W{κ2(C,N)-C(CH 2SiR3)=N-C(Me)=N(H)} (3, R = p-Tol) through a C-N coupling of nitrile molecules and migration of a silyl group.

AB - Treatment of Cp*(CO)2W(NCMe)Me (Cp* = η5-C5Me5) with HSiR3 (R = Et, p-Tol) afforded N-silylated η2-iminoacyl tungsten complexes Cp*(CO)2W{κ2(C,N)-C(Me)= N(SiR3)} (1a, R = Et; 1b, R = p-Tol). Analogous reactions in the presence of excess acetonitrile for a prolonged reaction time led to the formation of five-membered metallacycles Cp*(CO)2W{κ2(C,N)-C(Me)=N-C(Me) =N(H)} (2) and Cp*(CO)2W{κ2(C,N)-C(CH 2SiR3)=N-C(Me)=N(H)} (3, R = p-Tol) through a C-N coupling of nitrile molecules and migration of a silyl group.

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U2 - 10.1021/om700514d

DO - 10.1021/om700514d

M3 - Article

AN - SCOPUS:34548572088

SN - 0276-7333

VL - 26

SP - 4379

EP - 4382

JO - Organometallics

JF - Organometallics

IS - 18

ER -

Three- and five-membered W/C/N metallacycles formed by incorporation of acetonitrile molecules into silyltungsten intermediates

Abstract

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