Issue 3, 1981

Synthesis and reactivity of trinuclear osmium and dinuclear and trinuclear ruthenium compounds derived from hydroxyalkynes

Abstract

3-Hydroxy-3-methylbut-1-yne (HC[triple bond, length half m-dash]CCMe2OH) reacts with [Ru3(CO)12] to give [Ru3H(CO)9(C[triple bond, length half m-dash]CCMe2OH)] in very low yield as already described, but we can now report that the main products are isomeric compounds with empirical formula [Ru2(CO)6(alkyne)2], which contain ruthenacyclopentadiene groups, and substituted benzenes formed by oligomerisation of three alkyne molecules. Much better yields of [Os3H(CO)9(C2CMe2OH)] are obtained in a similar way with no evidence for alkyne trimerisation or complex dimer formation. The complex [Os3H2(CO)10] reacts at room temperature with HC2CMe2OH to give [Os3(CO)10(HC2CMe2OH)] and [Os3H(Co)10(CH[double bond, length half m-dash]CHCMe2OH)]. The dynamic n.m.r. behaviour of the first of these and the thermal decarbonylations of both are described. The 1H n.m.r. spectra of cationic clusters formed by hydroxide-ion loss in acidic solution are reported and the involvement of such cations in substitution and dehydration reactions of the η3 ligands.

Article information

Article type
Paper

J. Chem. Soc., Dalton Trans., 1981, 828-832

Synthesis and reactivity of trinuclear osmium and dinuclear and trinuclear ruthenium compounds derived from hydroxyalkynes

S. Aime and A. J. Deeming, J. Chem. Soc., Dalton Trans., 1981, 828 DOI: 10.1039/DT9810000828

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