过渡金属正离子和卡宾配合物成键特征的理论分析

在6—311C基组从头算的基础上对第一过渡系含偶数电子的金属正离子(Sc^+， V^+，Mn^+，Co^+，Cu^+)与卡宾CH2的配合物的成键特征进行了细致的分析。用能 级位移算符逐步降低分子片空轨道能级的方法代替分子片轨道冻结，使KSM能量分 解的耦合项得以消除。能量分析结果表明，Sc^+-CH2键是由σ供键，π供键与π反 馈键组成的，不能忽略π供键。而Cu^+-CH2键是由σ供键与σ，π反馈键组成的， 不能忽略σ反馈键。同时对VCH2^+，MnCH2^+和CoCH2^+的^1A1电子态也进行了粗略 的讨论。

Theoretical Analyses of Bond Character of Transition-Metal Ionswith Carbene Complexes

Ab initio MO calculations were carried out on transition-metal ions (Sc~+ , V~+ , Mn~+ , Co~+ , and Cu~+ ) with carbene (CH-2) at RHF/6- 311G level. In order to gain additional insight into the nature of bonding in these complexes, energy decomposition analyses were performed in detail using a one-electron shift operator. With this method the coupling term in the energy decomposition analyses could be eliminated completely. According to our calculations, the bond of Sc~ + -CH-2 formed by the a and TC donating interactions and the TT back- donating interaction, but the bond of Cu ~+ -CH is composed of the a donating interaction and the a and TT back-donating interactions. The bonds in other complexes were also discussed in brief.