Synthesis, structure and density functional study of the ansa-rhenocene complex [Re{(η-C5H4)CMe2(η-C5H4)}Cl]

Abstract

The ansa-rhenocene compound [Re{(η-C₅H₄)CMe₂(η-C₅H₄)}Cl] 1 has been prepared by reaction of ReCl₅ with [K₂(C₅H₄)CMe₂(C₅H₄)]. X-Ray crystallography shows the molecular structure to be unsymmetrical, with the angle defined by the Re-bridgehead carbon vector and the chlorine atom found to be 170.4°. A density functional study compares the electronic structure of [Re{(η-C₅H₄)CH₂(η-C₅H₄)}Cl] with [Re{(η-C₅H₅)₂Cl] and shows that for the ansa-bridged species, the chlorine binds less effectively in the central position. The calculated structure of [Re{(η-C₅H₄)CH₂(η-C₅H₄)}Cl] is also found to be unsymmetrical.