四核链型M—Fe—S(M=Mo,W)原子簇化合物的成键特征  

The Bonding Characteristics of Tetranuclear Linear Chain M—Fe—S (M=Mo, W) Cluster Compounds

作　　者：林性如[1] 林春森[1] 

机构地区：[1]福建师范大学实验中心

出　　处：《福建师范大学学报（自然科学版）》1993年第3期59-64,共6页Journal of Fujian Normal University：Natural Science Edition

摘　　要：用MAD—SCC—EHMO法计算了3个4核链型M—Fe—S(M=Mo,W)原子簇化合物[Fe_2S_2(MoS_4)_2]^(4-)、[Fe_2S_2(MoS_2O_2)_2]^(4-)和[Fe_2S_2(WS_4)_2]^(4-)的电子结构,根据计算所得的分子轨道能级、轨道特征和Mulliken约化重叠集居等数据,对其成键性质进行了分析。指出了在簇合物的成簇过程中,由于电子从Fe原子转移到M原子,使得簇合物中M的表观氧化态低于碎片M_2S_2X_2^(2-)中M的表观氧化态,本文还根据Mulliken约化重叠集居和电荷密度变化的分析,给出簇合物电子的离域性顺序([Fe_2S_2(MoS_4)_2]^(4-)>[Fe_2S_2(MOS_2O_2)_2]^(4-)>[Fe_2S_2(WS_4)_2]^(4-))。The electronic structures of three tetranuclear linear chain M—Fe—S (M=Mo, W) cluster compounds [Fe_2S_2(MoS_4)_2]^(4-)(?), [Fe_2S_2(MoS_2O_2)_2]^(4-)(?), and [Fe_2S_2(WS_4)_2]^(4-)(?) have been studied by using the MAD-SCC-EHMO method. The bonding properties are analyzed in terms of MO energies, MO characters, and Mulliken reduced overlap populations. In the process of cluster formation, it has been found that the formal oxidation state of M atom is lower in tetranuclear clusters than in fragments M S_2 X_2^(2-)(M=Mo, W; X=S, O) because of transference of electrons from Fe to M atom. Moreover, the intensity of electron delocalization was gave in the order[Fe_2S_2(MoS_4)_2]^(4-)>[Fe_2S_2(MoS_2O_4)_2]^(4-)>[Fe_2S_2(WS_4)_2]^(4-) according to analyzing the Mulliken reduced overlap populations and the changes of charge densities.

关 键 词：电子结构 EHMO 簇状化合物 铁 硫 

分 类 号：O641.4[理学—物理化学]