Title

A stable silylene in a reactive environment: Synthesis, reactivity, and silicon extrusion chemistry of a coordinatively unsaturated ruthenium silylene complex containing chloride and η3-P-C-P ligands

Document Type

Article

Publication Title

Organometallics

Publication Date

2-4-2002

Abstract

Reaction of [(dcypb)ClRu(μ-Cl)3Ru(dcypb)(N2)] (1) with 4 equiv of the stable silylene 1,3-di-tert-butyl-l,3,2-diazasilol-2-ylidene (SiL2N) yields coordinatively unsaturated RuCl(η3-dcypb)(SiL2N) (2). Complex 2 is a rare example of a trans-spanning diphosphine complex, this geometry resulting from an unprecedented attack of the metal on the tetramethylene ligand backbone. X-ray and solid-state 31P NMR and IR analysis reveal an agostic interaction between the metal and a silylene But group. In solution, this interaction is observed only at low temperature. Reaction of 2 with H2 containing trace H2O yields siloxane dimer [L2NSi-(H)]2O 3 and the ruthenium hydride-H2 adduct [(dcypb)(H)Ru(μ-Cl)2(μ-H)Ru(dcypb)(H2)] (4). Attempts to isolate 4 resulted in serendipitous crystallization of decomposition product 5, [(dcypb)(H)Ru(μ-Cl)3Ru(dcypb)(N2)]. X-ray analysis of 5 revealed a structure closely analogous to that of 4, in which bridging hydride is replaced by chloride, and η2-H2 by η2N2. Displacement of silylene from 2 is facile: treatment with 1 atm of CO affords free SiL2N, accompanied by RuCl(η3-dcypb)(CO)2 as a mixture of three isomers (6-8).

Volume

21

Issue

3

First Page

534

Last Page

540

DOI

10.1021/om0101801

ISSN

02767333

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