摘要
在 6 311G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VCH+ 2 ,MnCH+ 2 和CoCH+ 2 的1 A1
Ab initio MO calculations were carried out on transition-metal ions (Sc+, V+, Mn+, Co+, and Cu+) with carbene (CH2) at RHF/6-311 G 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+-CH2 formed by the sigma and pi donating interactions and the pi back-donating interaction, but the bond of Cu+-CH2 is composed of the a donating interaction and the sigma and pi back-donating interactions. The bonds in other complexes were also discussed in brief.
出处
《化学学报》
SCIE
CAS
CSCD
北大核心
2003年第2期161-165,共5页
Acta Chimica Sinica
关键词
过渡金属正离子
卡宾配合物
成键特征
能量分解分析
从头算
金属-碳键
transition-metal ions with carbene complex
bond character
energy decomposition analysis
ab initio MO calculation
