双核钼硫原子簇顺反异构体的定域化分子轨道研究

Studies on the Localized Molecular Orbital Properties for Syn and Anti Isomers of Dinuclear Mo-S Clusters

本文对簇合物离子[Mo_2(μ-S)_2S_2(S_2C_2H_4))_2]^(2-)的顺式和反式异构体进行了CNDO定域化计算,讨论了它的两种异构体的化学键性质,特别是Mo—Y(S)间的三重键性质.探讨了用亚层Mulliken布居数分析键的性质的可能性,并说明了这类簇离子多以顺式异构体存在的原因.

On the basis of summarization of structural properties of a series of cluster compounds with a core of [Mo2(μ-S)2Y2]2+ (Y=O or S),the syn and anti isomers of typical compound were calculated by using the CNDO SCF and E-R localization method.Their structures and bonding properties as well as the variety of Mo-Y(S) tribond with increasing the distance between Mo and S atoms were investigated.The inversion potential barrier between syn and anti isomers and the variance of molecular orbital properties were discussed.It is revealed that the molecular geometry factors play an important role in the formation of this barrier.