异核金属多重键配合物Cp2 MM'（μ-C8 H8）的理论研究

摘要

The structure and bonding of the heteronuclear metal-metal multiple bond complexes Cp2 MM’(μ-C8 H8 ) ( MM’=ScMn, TiCr, ScCo, TiFe, VMn) were theoretically studied. The calculated results shows that: ( 1 ) for the 28 ve systems, the ground-state of Cp2 V2 (μ-C8 H8 ) is triplet state with V-V triple bond, the isoelectronic Cp2 TiCr (μ-C8 H8 ) is singlet state with Ti-Cr quadruple bond, and the isoelectronic species Cp2 ScMn(μ-C8 H8 ) is singlet state with Sc-Mn triple bond. (2) For the 30 valence electron systems, the ground-states of Cp2 Cr2 (μ-C8 H8 ) is singlet state with Cr-Cr triple bond, the isoelectronic species Cp2 VMn(μ-C8 H8 ) is triplet state with V-Mn single bond, while the isoelectronic species Cp2 ScCo(μ-C8 H8 ) and Cp2 TiFe (μ-C8 H8 ) are singlet states with double metal-metal bond. In the triplet state of Cp2 MM’(μ-C8 H8 ) , the two metal atoms are generally 17-electron configuration, while in the singlet state, the two metal atoms are generally respectively 16-and 18-electron configuration.%研究了双核金属多重键配合物Cp2 MM'(μ-C8 H8)( MM'=ScMn, TiCr, ScCo, TiFe, VMn, VV, CrCr)的结构和成键模式。计算结果表明,对于28价电子体系, Cp2 V2(μ-C8 H8)基态为含V-V三重键的三态构型,其等电子体Cp2 TiCr(μ-C8 H8)为Ti-Cr四重键的单态,等电子体Cp2 ScMn(μ-C8 H8)为Sc-Mn三重键的单态。对于30价电子体系, Cp2 Cr2(μ-C8 H8)基态为含Cr-Cr三重键的单态,等电子体Cp2 VMn(μ-C8 H8)为含V-Mn单键的三态,等电子体Cp2 ScCo(μ-C8 H8)和Cp2 TiFe(μ-C8 H8)为含Sc-Co和Ti-Fe双键的单态。在三态Cp2 MM'(μ-C8 H8)中,两个金属原子多为17电子构型,而单态结构中两种金属原子多分别为16和18电子构型。