☆ 4.5 Article

Reactions of a Neutral Silylene Ruthenium Complex with Heterocumulenes: C=O Hydrosilylation of Isocyanates vs C=S Bond Cleavage of Isothiocyanate

ORGANOMETALLICS (2012)

Journal

ORGANOMETALLICS

Volume 31, Issue 2, Pages 527-530

Publisher

AMER CHEMICAL SOC

DOI: 10.1021/om2010854

Keywords

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Categories

Chemistry, Inorganic & Nuclear Chemistry, Organic

Funding

Ministry of Education, Culture, Sports, Science and Technology of Japan [18064003, 20038002, 21550054]
Grants-in-Aid for Scientific Research [18064003, 22350024, 24109011, 21550054, 20038002] Funding Source: KAKEN

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Abstract

Reactions of the neutral silylene ruthenium complex Cp*(CO)(H)Ru=Si(H){C(SiMe3)(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[kappa N-2,Si-N(Ar)=C(H)OSi(H)-{C(SiMe3)(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(SiMe3)(3)} (4). The structures of both types of products were unambiguously determined by X-ray crystallography.

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