The first isolation of an intermediate in the formation of a hexaruthenium carbido-cluster from the reaction of [Ru3(CO)12]: X-ray structure analyses of [Ru6(η2-µ4-CO)2(CO)13(η6-C6H3Me3)] and [HRu6(η2-µ4-CO)(CO)13(η7-µ2-C6H3Me2CH2)]

Abstract

Thermolysis of [Ru₃(CO)₁₂](1) in hydrocarbons heated under reflux containing excess of 1,3,5-trimethylbenzene(mesitylene) has yielded [Ru₆C(CO)₁₄(η⁶-C₆H₃Me₃)](2a) and two new hexaruthenium compounds [Ru₆(η²-µ₄-CO)₂(CO)₁₃(η⁶-C₆H₃Me₃)](3) and [HRu₆(η²-µ₄-CO)(CO)₁₃(η⁷-µ₂-C₆H₃Me₂CH₂)](4), shown by X-ray structure analyses to have metal frameworks previously unknown in ruthenium cluster chemistry; on further thermolysis the cluster (3) gives (2a) and is therefore the first intermediate in the well established conversion of triruthenium to hexaruthenium carbido-clusters to be identified.