双核簇合物M_2S_2(μ-S)_2(dtp)_2(M=Mo,W)的电子结构及元件组装活性的ab initio研究  

Ab Initio Studies on Electronic Structures and Unit Construction Reactivity of Dinuclear Complexes M_2S_2(μ-S)_2(dtp)_2 (M = Mo, W)

作　　者：陈瑞芝[1] 李隽[2] 刘春万[2] 蔡新华[1] 孟令鹏[1] 郑世钧[1] 

机构地区：[1]河北师范学院化学系计算量子化学研究室,石家庄050091 [2]中国科学院福建物质结构研究所,福州350002

出　　处：《化学学报》1995年第7期695-701,共7页Acta Chimica Sinica

基　　金：结构化学国家重点实验室和国家自然科学基金资助课题

摘　　要：本文对双核簇合物M_2S_2(μ-S)_2(dtp)_2(M=Mo,W)及其簇芯碎片M_2S_4^(2+)进行了相对论赝势从头算和Boys定域化分子轨道计算,根据所计算的正则分子轨道(CMO)和定域分子轨道(LMO)以及Mulliken布居分析,探讨了作为簇元元件的M_2S_4(dtp)_2的成键性质和电子结构,利用广义微扰理论,定性分析了M_2S_4^(2+)型簇合物的元件组装活性位和活性区,研究了它们发生[2+1]=3和[2+2]=4型元件组装的成簇机理.The electronic structure calculations have been carried out on two binuclear complexes Mo2S2(μ-S)2(dtp)2(1), W2S2(μ-S)2(dtp)2(2) and their core fragments Mo2S42+(3), W2S42+(4). The calculations were accomplished by using an ab initio quantum chemical method with relativistic effective core potentials. By the analysis of the calculated canonical molecular orbitals and localized molecular orbitals as well as the Mulliken populations, the bonding and electronic characteristics of these complexes have been studied. By virtue of the Generalized Purtubation theory, there activities and mechanism of M2S42+ complexes in forming the Cubane-like clusters via [2+2] fasion and the incomplete Cubane-type clusters via [2+1] fashion have been discussed. It is found that there exist three "Reactive Sites" and three "Reactive Regions" with higher electronic densities.

关 键 词：原子簇化合物 元件组装活性 成簇机理 

分 类 号：O641.4[理学—物理化学]