The Ditertiary-Phosphane-Bridged Heteronuclear Cluster RuOs3(μ-H)2(CO)9(μ-CO)2(μ-dppm): Synthesis and Reactivity with Alkynes

✍ Scribed by Yong Leng Kelvin Tan; Weng Kee Leong

• Publisher: John Wiley and Sons
• Year: 2007
• Tongue: English
• Weight: 271 KB
• Volume: 2007
• Category: Article
• ISSN: 1434-1948
• DOI: 10.1002/ejic.200601118

✦ Synopsis

Abstract

A high‐yielding alternative synthesis of the dppm‐bridged heteronuclear cluster RuOs~3~(μ‐H)~2~(CO)~9~(μ‐CO)~2~(μ‐dppm) (1) [dppm = bis(diphenylphosphanyl)methane] has been developed. Thermolysis of 1 resulted in dephenylation of both phosphane groups to afford the butterfly cluster RuOs~3~(CO)~12~(μ~4~,κ^2^:κ^2^‐PhPCH~2~PPh) (2). The reaction of 1 with selected alkynes afforded the products RuOs~3~(μ‐H)(CO)~8~(μ‐CO)(μ~3~,κ^2^:κ^1^‐PhPCH~2~PPh~2~)(μ~3~,η^1^:η^2^:η^1^‐L) (3) (L = alkyne) in which the alkyne is aligned parallel to an Os–Os bond(// Os‐Os isomer). The clusters incorporating internal alkynes underwent isomerization to the //Ru‐Os isomer by alkyne and hydride migration. Several other cluster products of these reactions were also identified, including RuOs~3~(μ‐H)(CO)~8~(μ‐CO)(μ~3~,κ^2^:κ^1^‐PhPCH~2~PPh~2~)(μ~3~,η^1^:η^2^:η^1^‐__t__BuC~2~CHO)(6) in which the methyl group of the alkyne has been oxidized to an aldehyde. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)