STRUCTURE AND CHEMISTRY OF BIS(CYCLOPENTADIENYL)-MLN COMPLEXES
STRUCTURE AND CHEMISTRY OF BIS(CYCLOPENTADIENYL)-MLN COMPLEXES
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DOI：
10.1021/ja00423a017
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发表时间：
1976-01-01
影响因子：
15
通讯作者：
HOFFMANN, R
中科院分区：
文献类型：
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作者：
LAUHER, JW;HOFFMANN, R
弯曲的双（jj 5-xm）M片段CpaM（M=过渡金属）的分子轨道的构造用作Cp 2 ML n分子的电子结构的一般说明的起始点。本文分析了下列问题：Cp_2ML_n的几何构型与d电子构型的关系;与受体和供体配体的键合，强调了轨道相互作用与构象的关系，如烯烃和卡宾的取向和二硫纶的弯曲; Cp_2M部分的畸变;配位烯烃的插入反应;羰基插入反应;氧化偶联;烯丙基和四氢硼酸盐络合物;弯曲的双（ir-bis）过渡金属络合物1的显著丰富的化学性质是本研究的焦点。我们继续制定这样的分子的电子结构的模型，并将该模型与各种已知的复杂类型和已知的结构。最终的目标是了解这些分子的化学性质。
A construction of the molecular orbitals of a bent bis (jj5-cyclopentadienyl) M fragment, CpaM, M= a transition metal, serves as a starting point for a general account of the electronic structure of Cp2ML „molecules,= 1-3. The following problems are analyzed: the geometry of Cp2ML „as a function of the d electron configuration; bonding with accep-tor and donor ligands, emphasizing orbital interactions with conformational consequences such as olefin and carbene orientation and dithiolene bending; distortions of the CP2M moiety; insertion reactions of coordinated olefins; carbonyl insertion re-actions; oxidative coupling; allyl and tetrahydroborate complexes; triscyclopentadienyl complexes.The remarkably rich chemistry of bent bis (ir-cyclopentadienyl) transition metal complexes1 is the focus of this study. We proceed to formulate a model for the electronic structure of such molecules, and relate that model to the various known complex types, and the known structures. The eventual goal is an understanding of the chemistry of these molecules.