A Stable Silylene in a Reactive Environment: Synthesis, Reactivity, and Silicon Extrusion Chemistry of a Coordinatively Unsaturated Ruthenium Silylene Complex Containing Chloride and 
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- 作者：Dino Amoroso ; Michael Haaf ; Glenn P. A. Yap ; Robert West ; and Deryn E. Fogg
- 刊名：Organometallics
- 出版年：2002
- 出版时间：February 4, 2002
- 年：2002
- 卷：21
- 期：3
- 页码：534 - 540
- 全文大小：109K
- 年卷期：v.21,no.3(February 4, 2002)
- ISSN：1520-6041
文摘
Reaction of [(dcypb)ClRu(
-Cl)3Ru(dcypb)(N2)] (1) with 4 equiv of the stable silylene 1,3-di-tert-butyl-1,3,2-diazasilol-2-ylidene (SiLN2) yields coordinatively unsaturated RuCl(
3-dcypb)(SiLN2) (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 tetramethyleneligand backbone. X-ray and solid-state 31P NMR and IR analysis reveal an agostic interactionbetween the metal and a silylene But group. In solution, this interaction is observed only atlow temperature. Reaction of 2 with H2 containing trace H2O yields siloxane dimer [LN2Si(H)]2O 3 and the ruthenium hydride-H2 adduct [(dcypb)(H)Ru(-Cl)2(-H)Ru(dcypb)(H2)](4). Attempts to isolate 4 resulted in serendipitous crystallization of decomposition product5, [(dcypb)(H)Ru(-Cl)3Ru(dcypb)(N2)]. X-ray analysis of 5 revealed a structure closelyanalogous to that of 4, in which bridging hydride is replaced by chloride, and 2-H2 by 2-N2. Displacement of silylene from 2 is facile: treatment with 1 atm of CO affords free SiLN2,accompanied by RuCl(3-dcypb)(CO)2 as a mixture of three isomers (6-8).
-Cl)3Ru(dcypb)(N2)] (1) with 4 equiv of the stable silylene 1,3-di-tert-butyl-1,3,2-diazasilol-2-ylidene (SiLN2) yields coordinatively unsaturated RuCl(3-dcypb)(SiLN2) (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 tetramethyleneligand backbone. X-ray and solid-state 31P NMR and IR analysis reveal an agostic interactionbetween the metal and a silylene But group. In solution, this interaction is observed only atlow temperature. Reaction of 2 with H2 containing trace H2O yields siloxane dimer [LN2Si(H)]2O 3 and the ruthenium hydride-H2 adduct [(dcypb)(H)Ru(-Cl)2(-H)Ru(dcypb)(H2)](4). Attempts to isolate 4 resulted in serendipitous crystallization of decomposition product5, [(dcypb)(H)Ru(-Cl)3Ru(dcypb)(N2)]. X-ray analysis of 5 revealed a structure closelyanalogous to that of 4, in which bridging hydride is replaced by chloride, and 2-H2 by 2-N2. Displacement of silylene from 2 is facile: treatment with 1 atm of CO affords free SiLN2,accompanied by RuCl(3-dcypb)(CO)2 as a mixture of three isomers (6-8).