多中心d-pπ键与高氧化态钼簇合物的几何构型——(Ⅰ)“碎片结构”模型及分子轨道研究  

The Multiple Center d-p π Bond and the Configuration of Molybdenum Cluster Compounds in Higher Oxidation States (Ⅰ) "Fragmental Structer" Model and Research of Molecular Orbital

作　　者：李俊篯[1] 黄金陵[2] 

机构地区：[1]福州大学化学系 [2]中国科学院福州结构化学开放研究实验室,福州350002

出　　处：《Chinese Journal of Structural Chemistry》1990年第4期249-257,共9页结构化学（英文）

摘　　要：本文通过对不同构型的二核钼簇合物簇胳结构的分子轨道计算,揭示了Mo—B(T)原子间的多中心d-p π键与该结构的稳定性及结构参数α、θ和R之间的内在联系,提出了2～6核高氧化态钼簇合物的簇胳由“碎片结构”组合而成的设想,该模型对以μ_2-S_2为桥的三核钼簇合物中的“共面—异面”规则和簇胳为[Mo_4S_3O]^(6+)的钼簇中的反常Mo—Mo键距给出合理解释,确认了桥原子对Mo—Mo键长和键强的决定作用。In this paper,the internal relations between the multiple centre d-p π bonding of the Mo -B(T)atoms and the structural stability, as well as the structural parameters a, θ and R have been revealed,and a block-building conception from the 'fragmental structure' for the cluster skeleton of 2-6 nuclear Mo clusters in higher oxidation states has been elucidated by the MO calculation ofthe cluster skeleton with various bridging atoms and α,θ values.Based on the model, several reasonable interpretations have been given for the 'in- and out- of plane' rule in the trinuclear Mo clusters with μ2-S2 and the anomalous bond length (Mo-Mo) of some clusters with a core [Mo4S3O]6+. It is confirmed that the indirect bonding through bridge atoms is the primary influence factor for the R(Mo-Mo) and Mo-Mo bond strength.

关 键 词：多中心d-pπ键 几何构型 分子轨道 高氧化态钼簇合物 二元簇合物 

分 类 号：O614.612[理学—无机化学] O641.1[理学—化学]