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首页> 外文期刊>Chemistry: A European journal >'Bent Bonds' between Bismuth and Carbon Atoms as a Result of C-H Activation in Mo-Bi Complexes
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'Bent Bonds' between Bismuth and Carbon Atoms as a Result of C-H Activation in Mo-Bi Complexes

机译：Mo-Bi配合物中C-H活化导致铋和碳原子之间的“弯曲键”

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摘要

The reaction of molybdo-cenedihydride with two equivalents of[Bi(O/Bu)3]proceeds via alcohol elimination and provides the compound[Cp2Mo{Bi(OrBu)_2}2](1),which contains two Mo-Bi metal bonds,in good yields.If the two reagents are employed in a 1:1 ratio continuative condensation reactions occur.These initially lead to[{Cp2Mo}2{u.-Bi(OfBu)}2](2),which,however,is very unstable in solution and decomposes via additional alcohol elimination:Complex-induced proximity effects facilitate the cleavage of C-H bonds within the cyclopenta-dienyl ligands by the residual alkoxide ligands,so that spontaneously two further equivalents of alcohol are released,thereby yielding two isomeric compounds 3 and 4 with Cp ligands bridging Mo~Bi metal bonds:The first isomer(3)contains two u2-r)5:r)1-C_5H4 ligands,the second isomer(4)contains one bridging Ug-^V^'-CsH,ligand.The binding of these ligands to molybdenum and bismuth atoms at the same time is made possible through "bent bonds" between the bismuth and certain carbon centres.These unusual bonding situations were analysed by means of calculations based on density functional theory(DFT),the atoms in molecules(AIM)theory,natural bond order(NBO)considerations and the electron localisation function(ELF).According to the results the bonds can be understood in terms of carbanionic centres interacting with bismuth cations(i.e.closed-shell interactions).The formation of these bonds and the thermodynamics/kinetics involved on going from 2 to 3 and 4 were also studied by theoretical methods,so that the product formation is rationalised.The crystal structures of all four new compounds were determined.These structures but also the properties and mechanisms of formation are discussed against the background of the corresponding results obtained while studying the system[McCp2MoH_2]/[Bi(OrBu)3].
机译：钼-乙酰二氢化物与两当量的[Bi（O / Bu）3]的反应是通过醇消除反应完成的，并提供了包含两个Mo-Bi金属键的化合物[Cp2Mo {Bi（OrBu）_2} 2]（1）如果以1：1的比例使用两种试剂，则会发生连续缩合反应。它们最初会导致[{Cp2Mo} 2 {u.-Bi（OfBu）} 2]（2），但是，在溶液中非常不稳定并通过额外的醇消除而分解：络合物诱导的邻近效应促进残留的醇盐配体裂解环戊二烯基配体中的CH键，从而自发释放出另外两个当量的醇，从而生成两个异构体具有连接Mo〜Bi金属键的Cp配体的化合物3和4：第一异构体（3）包含两个u2-r）5：r）1-C_5H4配体，第二异构体（4）包含一个桥接Ug- ^ V ^'这些配体同时通过钼和铋之间的“弯曲键”结合到钼原子和铋原子上。通过基于密度泛函理论（DFT），分子中原子（AIM）理论，自然键序（NBO）和电子定位功能（ELF）的计算，分析了这些不寻常的键合情况。结果可以通过碳负离子中心与铋阳离子相互作用（即闭壳相互作用）来理解键。还通过理论方法研究了这些键的形成以及从2到3和4的热力学/动力学，确定了这四种新化合物的晶体结构。在研究系统[McCp2MoH_2] / [Bi（）时，以得到的相应结果为背景，讨论了这些结构以及形成的性质和机理。 OrBu）3]。

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