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

摘要

The ansa-rhenocene compound [Re{(eta-C5H4)CMe2(eta-C5H4)}Cl] 1 has been prepared by reaction of ReCl5 with [K-2(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 degrees. A density functional study compares the electronic structure of [Re{(eta-C5H4)CH2(eta-C5H4)}Cl] with [Re{(eta-C5H5)(2)Cl] and shows that for the ansa-bridged species, the chlorine binds less effectively in the central position. The calculated structure of [Re{(eta-C5H4)CH2(eta-C5H4)}Cl] is also found to be unsymmetrical. [References: 25]