Electronic structure of the electron-poor dinuclear organometallic compounds [(CpM)(CpM ')mu-Cot (M, M ' = V, Cr, Fe, Co)

摘要

A systematic theoretical investigation of a variety of synfacial homo- and heterodinuclear organometallic compounds [(CpM)(CpM')]mu-Cot (Cot = cyclooctatetraene; Cp = cyclopentadienyl) is presented. These compounds show, depending on the metals M and M', a number of remarkable and even surprising properties, concerning the metal-metal distances, the magnetic behavior and the spin density distribution. Based on the results of CASSCF calculations, a so-called twinnocene model has been developed, which considers the dinuclear systems as being composed of two separated metallocene-like subunits. The formally nonbonding metal 3d electrons of the subunits interact or do not interact, respectively, in a very specific and characteristic way, to form the dimetal moieties. The model describes the electronic structure, the bonding properties and the wide range of the experimental findings for the whole class of compounds. The strategy followed in the course of the study can be generally recommended for the investigation of dinuclear transition metal complexes. [References: 36]