腈与氢化（硅烯基）钨配合物的化学计量硅氢化反应：W-Si-N三元环配合物的形成及其独特的热行为。

Stoichiometric hydrosilylation of nitriles with hydrido(hydrosilylene)tungsten complexes: formation of W-Si-N three-membered ring complexes and their unique thermal behaviors.

作者信息

Watanabe Takahito, Hashimoto Hisako, Tobita Hiromi

机构信息

Department of Chemistry, Graduate School of Science, Tohoku University, Aoba-ku, Sendai 980-8578, Japan.

出版信息

J Am Chem Soc. 2006 Feb 22;128(7):2176-7. doi: 10.1021/ja056715p.

DOI:10.1021/ja056715p

PMID:16478147

Abstract

Reactions of hydrido(hydrosilylene)tungsten complexes, Cp'(CO)2(H)W=Si(H)[C(SiMe3)3], with nitriles (MeCN, tBuCN) at 60 degrees C gave hydrosilylation products, Cp'(CO)2W[kappa2(N,Si)-Si(H)(N=CHR'){C(SiMe3)3}] (R' = Me, tBu), with a novel W-Si-N three-membered ring structure. The product of the hydrosilylation of tBuCN underwent reversible rearrangement at 70 degrees C to a silylene complex, Cp'(CO)2(H)W=Si(N=CHtBu)[C(SiMe3)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.

摘要

氢化（硅烯基）钨配合物Cp'(CO)2(H)W=Si(H)[C(SiMe3)3]在60℃下与腈类（乙腈、叔丁腈）反应生成氢化硅烷化产物Cp'(CO)2W[kappa2(N,Si)-Si(H)(N=CHR'){C(SiMe3)3}]（R' = 甲基、叔丁基），其具有新颖的W-Si-N三元环结构。叔丁腈氢化硅烷化的产物在70℃下可逆重排为硅烯配合物Cp'(CO)2(H)W=Si(N=CH叔丁基)[C(SiMe3)3]，该配合物是平衡体系中的主要成分。提出了氢化硅烷化的反应机理，包括腈类与硅烯配体的配位以及随后氢配体向腈类碳的迁移。