Synthetic, Structural, and Kinetic Studies of [CpRu(CO)₂(μ₂-η¹(S):η⁶-DBT)RuCp*][PF₆]₂:  A Dibenzothiophene Bridge between Two Ruthenium Fragments

Abstract

The complexes [CpRu(CO)2(μ2-η1(S):η6-DBT)RuCp‘]2+ (Cp‘ = η5-C5H5 (3), η5-C5Me5 (4)) were synthesized and shown by X-ray crystallography to contain a bridging dibenzothiophene ligand that is coordinated to {CpRu(CO)2}+ through the sulfur atom and to {Cp‘Ru}+ through an arene ring (η6). Kinetic studies of the displacement of the [Cp*Ru(η6-DBT)]+ moiety in 4 by P(OPh)3 show that the η6-coordinated {Cp*Ru}+ group weakens the Ru−S bond, as compared to that in [CpRu(CO)2(η1(S)-DBT)]+, and greatly increases the rate of DBT dissociation.