Reactions of a neutral silylene ruthenium complex with heterocumulenes: C=o hydrosilylation of isocyanates vs c=s bond cleavage of isothiocyanate

Mitsuyoshi Ochiai; Hisako Hashimoto; Hiromi Tobita

doi:10.1021/om2010854

Reactions of a neutral silylene ruthenium complex with heterocumulenes: C=o hydrosilylation of isocyanates vs c=s bond cleavage of isothiocyanate

Mitsuyoshi Ochiai, Hisako Hashimoto, Hiromi Tobita

SCI - Chemistry

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

30 Citations (Scopus)

Abstract

Reactions of the neutral silylene ruthenium complex Cp*(CO)(H)Ru= Si(H){C(SiMe ₃₎₃} (2) with heterocumulenes were investigated. Treatment of 2 with ArNCO (Ar = Mes, Ph; Mes = 2,4,6-trimethylphenyl) resulted in hydrosilylation of ArNCO selectively at the C=O bond at room temperature to give the five-membered chelate complexes Cp*(CO)Ru[κ2N,Si-N(Ar)=C(H) OSi(H)- {C(SiMe ₃₎₃}] (3a, Ar = Mes; 3b, Ar = Ph). In contrast, the reaction of 2 with MesNCS led to cleavage of the C=S double bond to give the isocyanide complex Cp*(CO)Ru(CNMes){SSiH2C(SiMe ₃₎₃} (4). The structures of both types of products were unambiguously determined by X-ray crystallography.

Original language	English
Pages (from-to)	527-530
Number of pages	4
Journal	Organometallics
Volume	31
Issue number	2
DOIs	https://doi.org/10.1021/om2010854
Publication status	Published - 2012 Jan 23

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Reactions of a neutral silylene ruthenium complex with heterocumulenes: C=o hydrosilylation of isocyanates vs c=s bond cleavage of isothiocyanate",

abstract = "Reactions of the neutral silylene ruthenium complex Cp*(CO)(H)Ru= Si(H){C(SiMe 3)3} (2) with heterocumulenes were investigated. Treatment of 2 with ArNCO (Ar = Mes, Ph; Mes = 2,4,6-trimethylphenyl) resulted in hydrosilylation of ArNCO selectively at the C=O bond at room temperature to give the five-membered chelate complexes Cp*(CO)Ru[κ2N,Si-N(Ar)=C(H) OSi(H)- {C(SiMe 3)3}] (3a, Ar = Mes; 3b, Ar = Ph). In contrast, the reaction of 2 with MesNCS led to cleavage of the C=S double bond to give the isocyanide complex Cp*(CO)Ru(CNMes){SSiH2C(SiMe 3)3} (4). The structures of both types of products were unambiguously determined by X-ray crystallography.",

author = "Mitsuyoshi Ochiai and Hisako Hashimoto and Hiromi Tobita",

year = "2012",

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T2 - C=o hydrosilylation of isocyanates vs c=s bond cleavage of isothiocyanate

AU - Ochiai, Mitsuyoshi

AU - Hashimoto, Hisako

AU - Tobita, Hiromi

PY - 2012/1/23

Y1 - 2012/1/23

N2 - Reactions of the neutral silylene ruthenium complex Cp*(CO)(H)Ru= Si(H){C(SiMe 3)3} (2) with heterocumulenes were investigated. Treatment of 2 with ArNCO (Ar = Mes, Ph; Mes = 2,4,6-trimethylphenyl) resulted in hydrosilylation of ArNCO selectively at the C=O bond at room temperature to give the five-membered chelate complexes Cp*(CO)Ru[κ2N,Si-N(Ar)=C(H) OSi(H)- {C(SiMe 3)3}] (3a, Ar = Mes; 3b, Ar = Ph). In contrast, the reaction of 2 with MesNCS led to cleavage of the C=S double bond to give the isocyanide complex Cp*(CO)Ru(CNMes){SSiH2C(SiMe 3)3} (4). The structures of both types of products were unambiguously determined by X-ray crystallography.

AB - Reactions of the neutral silylene ruthenium complex Cp*(CO)(H)Ru= Si(H){C(SiMe 3)3} (2) with heterocumulenes were investigated. Treatment of 2 with ArNCO (Ar = Mes, Ph; Mes = 2,4,6-trimethylphenyl) resulted in hydrosilylation of ArNCO selectively at the C=O bond at room temperature to give the five-membered chelate complexes Cp*(CO)Ru[κ2N,Si-N(Ar)=C(H) OSi(H)- {C(SiMe 3)3}] (3a, Ar = Mes; 3b, Ar = Ph). In contrast, the reaction of 2 with MesNCS led to cleavage of the C=S double bond to give the isocyanide complex Cp*(CO)Ru(CNMes){SSiH2C(SiMe 3)3} (4). The structures of both types of products were unambiguously determined by X-ray crystallography.

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