系列含二核钼(钨、铬)簇阴离子化合物的理论研究

摘要

在密度泛函B3LYP/SDD水平下,本文对9种[(M2OnS4-n)(i-mnt)2]2-(M=Cr,Mo,W; i-mnt=S2C=C(CN)2-2 ;n=0,1,2)二核簇阴离子的配合物结构进行了全自由度优化,并计算了键长、键角、自然价键轨道NBO等数据.通过对其几何结构和成键特征的理论分析表明两金属原子之间存在M-M金属键,i-mnt配体中存在离域的π电子.轨道分析表明金属原子存在的空d轨道可以通过接受氧或硫的孤电子对形成超分子化合物.%The structures of nine cluster compounds with [(M2OnS4-n)(i-mnt)2]2- (M=Cr, Mo, W; i-mnt=S2 C=C ( CN ) 2-2 ; n=0 , 1 , 2 ) as the cluster anion were fully optimized by using B3 LYP method at the basis of SDD. The bond lengths, bond angles, Natural Bond Orbital analysis ( NBO) of cluster compounds were obtained.By analyzing geometry structures and bonding properties, it was proposed that M-M bond existed by the interaction between the two metals and the delocalization of π electrons existed indeed in i-mnt ligand. Orbital analysis indicated that vacant d orbital existed in the metal thus form supermolecular compound by accepting the lone electron pair of oxygen or sulfur.