钌硅烯配合物的合成与结构：N-杂环硅烷中Si-Cl键的活化

Synthesis and structure of ruthenium-silylene complexes: activation of Si-Cl bonds in N-heterocyclic silanes.

作者信息

Yoo Hyojong, Carroll Patrick J, Berry Donald H

机构信息

Department of Chemistry and Laboratory for Research on the Structure of Matter, University of Pennsylvania, Philadelphia, Pennsylvania 19104-6323, USA.

出版信息

J Am Chem Soc. 2006 May 10;128(18):6038-9. doi: 10.1021/ja0580744.

DOI:10.1021/ja0580744

PMID:16669664

Abstract

Ru(0) complexes of bis(imino)pyridine ligands, [eta2-N3]Ru(eta6-Ar) and {[N3]Ru}2(mu-N2), where Ar = C6H6 or C6H5Me and [N3] = 2,6-(MesN=CMe)2C5H3N, react with N-heterocyclic silicon(IV) compounds to yield Ru(II) silylene complexes of the type [N3]Ru(X)(Cl){Si(NN)} (X = H, Cl, and Si(NN) = N,N'-bis(neopentyl)-1,2-phenylenedi(amino)silylene). The activation of two groups on the silane occurs in a stepwise fashion: initial oxidative addition of a Si-X bond, followed by 1,2-migration (alpha-elimination) of the Si-Cl group to the metal. Reversible dissociation from the Ru(II) center leads to free silylene, which can be preferentially trapped with Ru(0) complexes to generate a zero-valent silylene complex, [N3]Ru(N2){Si(NN)}, which also contains a terminal dinitrogen ligand.

摘要

双（亚氨基）吡啶配体的Ru(0)配合物，即[η2-N3]Ru(η6-Ar)和{[N3]Ru}2(μ-N2)，其中Ar = C6H6或C6H5Me且[N3] = 2,6-(MesN=CMe)2C5H3N，与N-杂环硅（IV）化合物反应生成类型为[N3]Ru(X)(Cl){Si(NN)}的Ru(II)硅烯配合物（X = H、Cl，且Si(NN) = N,N'-双（新戊基）-1,2-苯二（氨基）硅烯）。硅烷上两个基团的活化以逐步方式发生：首先是Si-X键的氧化加成，接着是Si-Cl基团向金属的1,2-迁移（α-消除）。从Ru(II)中心的可逆解离会产生游离硅烯，其可优先被Ru(0)配合物捕获以生成零价硅烯配合物[N3]Ru(N2){Si(NN)}，该配合物也含有一个末端二氮配体。