| 一些多层夹心配合物的电子结构和成键 |
| ELECTRONIC STRUCTURE AND BONDING OF SOME OLIGODECKER SANDWICH COMPLEXES |
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| 摘要: 本文采用Fenske-Hall方法研究了三层和四层夹心配合物的电子结构和成键.结果指山,三层夹心配合物的稳定电子组态为30-34价电子(VE),但是当金属-金属间距缩短时,由两个过渡金属的dx2,dx2-y2,和dxy组成的三个MO能级上升且定位在前线轨道区域,因此预料26-28VE也是稳定电子组态.基于MO分析,42VE的四层夹心酏合物是稳定电子组态,然而由于HOMO(dx2)与LUMO(并轨道dxy,dxz)的能隙不大.最大价电子数为46的这类化合物也可稳定存在.从MO图得知.四层夹心配合物的前线轨道是由过渡金属的5根d轨道所组成.因此预料可以制备出价电子我从36VE变化到46VE的这类化合物.根据MO图和微扰理论,配合物[(η5-C5H5)Fe(μ,η5-C3B2H5)Co(η5-C5H5)]+和[(η5-C5H5)Fe(μ,η5-C3B2H5)Fe(η5-C5H5)]的EPR给予了合理的解释. |
| 关键词: 多层夹心配合物 MO EPR |
| 基金项目: |
| Abstract: The electronic structure and bonding of triple-decker and tetradeeker sandwich complexes have been studied by the Fenske-Hall method. The results show that the stable electronic configurations of triple-decker complexes have 30 to 34 VE, first calculated by R. Hoffmann. Howevct, the configurations with 26 to 29 VE arc also stable as the M-M distance is shortencd.The enctgy lcvcls of three d orbitals made up of dz2, dx2-y2 and dxy orbitals of the two transition metals arc rised and located in the frontier region. Based on a MO analysis.tetradccker complexes with 42 VE have a stable clccironic configuration. However, because the splitting energy between HOMO(dx2 orbital)and Received date 1994-l I-22.This work was supported by Nahonal Natural Science Fundation.Zhu Longgcn, male, ago of 55, profCSsor. mainly work on theoretical coordlnahon chemistry and bioinoreanicchemistry.LUMO(degenerate orbitals dxy dxz)is not large, complexes with 46 VE, which represents the maximum number of valence electrons for this series, are also stable. Because the frontier orbitals of the tetradecker complexes are made up of five d orbitals of the transition metals, a series of trinuclcar complexes with 36 VE to 46 VE is expected. In the light of MO diagrams and perturbation theory, the EPR of the complexes [(η5-C5H5)Fe(μ,η-C3B2H5)Co(η5C5H5)]+ and [(η5-C5H5)Fe(μ,η-C3B2H5)Fe(η5-C5H5)]can be reasonably explained. |
| Keywords: tripledecker tetradecker MO calculations EPR |
| 投稿时间：1994-11-22 |
| 摘要点击次数: 1143 |
| 全文下载次数: 1083 |
| 朱龙根,Walter Siebert,Hubert Wadepohl.一些多层夹心配合物的电子结构和成键[J].无机化学学报,1995,11(4):337-350. |
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