排序方式: 共有21条查询结果,搜索用时 15 毫秒
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以HF/6-311+G^*基组研究了过渡金属硅烯离子MSiH^+2(M从Sc至Cu)的构型、成键特征以及M-Si键解离能。具有共平面构型的MSiH^+2,其M=Si键带有明显的双键特征,M=Si键解离能从Sc至Cu呈现周期性变化,与M的金属离子激发能有近似的线性关系。 相似文献
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用从头计算法计算了各种取代的锂卡宾正离子XCHLi+(X=OH,NH2,CH2CH,NC,C6H5)相对于锂卡宾正离子CH2Li+的稳定化能,并讨论了稳定化能和它们分子轨道的关系。具有π给予功能的取代基,在其共平面分子构型中,由于和卡宾碳和锂原子空轨道形成二电子多中心共轭分子轨道,因而具有最大的稳定作用。相反,在相应的正交构型中,稳定作用则较小。同时具有π给予和σ接受效应的取代基,π给予起主导作用。仅有σ接受功能的取代基,则有去稳定作用。考察它们的LUMO特点,发现它们具有较高的亲电反应性能。 相似文献
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Ab initio study of the transition-metal carbene cations 总被引:3,自引:0,他引:3
The geometries and bonding characteristics of the first-row transition-metal carbene cations MCH_2~ were investigated by ab initio molecular orbital theory (HF/LANL2DZ). All of MCH_2~ are coplanar. In the closed shell structures the C bonds to M with double bonds; while in the open shell structures the partial double bonds are formed, because one of the σ and π orbitals is singly occupied. It is mainly the π-type overlap between the 2p_x orbital of C and 4p_x, 3d_(xz), orbitals of M~ that forms the π orbitals. The dissociation energies of C—M bond appear in periodic trend from Sc to Cu. Most of the calculated bond dissociation energies are close to the experimental ones. 相似文献
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用从头算分子轨道理论,研究了不同卤代数卡宾CHClFLi的结构和稳定性,优化得到4种平衡构型和相应过渡态地各构型的特别进行了分析,并与相同卤代类卡宾做了比较。 相似文献
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过渡金属卡宾正离子的从头算研究 总被引:3,自引:1,他引:2
过渡金属卡宾正离子被认为是如烯烃的聚合和烷基金属的分解过程等许多反应的中间体.较为稳定的环丁烷金属离子和环戊烷金属离子已从相应酮的脱羰反应获得[1].Jacobson等[2]研究了FeCH+2和CoCH+2与烯烃和环烷烃的气相反应.Mckee[3]在... 相似文献
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The geometries and bonding characteristics of the complexes of the first-row transition-metal ions with CH, CH_2 and CH_3 were investigated by ab initio molecular orbital theory. MCH~ and MCH_2~ are linear and coplanar, re spectively. Both of them are with obvious treble or double bond characteristics, but these multiple bonds are mostly "im perfect". The calculated bond dissociation energies of C--M~ , C=M~ and C≡M~ are mostly close to the experi mental values, and appear in similar periodic trends from Sc to Zn. 相似文献
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