Ab Initio MO Study on Cationic Phosphenium Complexes of Group 6 Transition Metals, fac- and mer-[(bpy)(CO)3M{PN(Me)CH2CH2NMe}]+ (M = Mo, W)
Ab Initio MO Study on Cationic Phosphenium Complexes of Group 6 Transition Metals, fac- and mer-[(bpy)(CO)3M{PN(Me)CH2CH2NMe}]+ (M = Mo, W)
复制标题
第 6 族过渡金属阳离子磷配合物的从头开始 MO 研究，fac- 和 mer-[(bpy)(CO)3M{PN(Me)CH2CH2NMe}] (M = Mo, W)
DOI：
10.1021/om000233z
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发表时间：
2000
期刊：
影响因子：
2.8
通讯作者：
Tsuneo Hirano
中科院分区：
文献类型：
--
作者：
K. Takano;H. Tsumura;H. Nakazawa;and Misako Kurakata;Tsuneo Hirano
本文报道了在RHF理论水平上用金属的有效核势（ECP）和几种全电子基组对第6族过渡金属阳离子膦配合物（M = Mo，W）的面异构体和面异构体的量子力学从头计算.完全优化的几何形状使用ECP由史蒂文斯等人。是在良好的协议与相关的复杂的实验参数。理论预测的相对热力学稳定性的钼和钨的配合物的邻位异构体和面异构体也符合实验行为。通过结构分析、M-P（Phosphenium）键的转动行为以及中心部分原子的Mulliken电荷和轨道布居分析表明：（i）Phosphenium配体具有较强的π电子接受特性，比CO配体强;（ii）Phosphenium配体的π电子主要来自过渡金属，而很少来自氨基.
Quantum mechanical ab initio calculations at the RHF level of theory using effective core potentials (ECP) for the metals and several all-electron basis sets are reported for the facial and meridional isomers of cationic phosphenium complexes of group 6 transition metals, (M = Mo,W). Fully optimized geometries using the ECP by Stevens et al. are in good agreement with the experimental parameters for the related complex. The theoretically predicted relative thermodynamic stability of the meridional and facial isomers of Mo and W complexes also agrees well with experimental behavior. Structural consideration, M−P(phosphenium) bond rotational behavior, and Mulliken charge and orbital population analysis of component atoms in the central part based on the computational results reveal that (i) a phosphenium ligand has strong π-electron accepting character, which is stronger than that of a CO ligand, and (ii) a phosphenium ligand gets π-donation predominantly from a transition metal and little from amino groups...