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首页> 外文期刊>Coordination chemistry reviews >Activation of alkynes by diphosphine- and mu-phosphido-spanned heterobimetallic complexes
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Activation of alkynes by diphosphine- and mu-phosphido-spanned heterobimetallic complexes

机译：二膦和μ-膦跨异双金属配合物活化炔烃

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This review deals with the coordination of alkynes as reactive unsaturated substrates on heterobimetallic transition metal complexes LnM-M'L in which two transition metal centers interact through a metal metal bond spanned by a diphosphane ligand such as bis(diphenylphoshino)methane or a bridging phosphido group of the type mu-PR2. Presented are few examples featuring simple pi-coordination of the alkyne on M or M', but the majority of examples involve bimetallic activation associated with synergetic effects of the two adjacent metal centers giving rise to dimetallatetrahedranes, dimetallacyclobutenes, dimetallated olefins, mu-vinylidenes and acetylides species. Covered are also heterobimetallic systems, in which carbon-carbon or carbon-phosphorus couplings have occurred between two alkyne ligands or with carbonyl groups and P-donor ligands present in the coordination sphere of the heterodinuclear scaffold. Furthermore, hydrometallation reactions leading to vinyl-species through insertion of R-C equivalent to C-H or R-C equivalent to C-R into a terminal or bridging M-H bond are presented. Included in this review are also selected examples of reactivity studies and transformation of the initially formed heterobimetallic alkyne species, such as addition of electrophiles (H+,R+), generating heterometallic alkenyl and mu-eta(1):eta(2)-allenyl salts. (C) 2017 Elsevier B.V. All rights reserved.
机译：这项审查处理炔作为异双金属过渡金属配合物LnM-M'L上的反应性不饱和底物的配位，其中两个过渡金属中心通过由二膦配体（例如双（二苯基膦基）甲烷或桥连的磷基）跨越的金属键相互作用mu-PR2类型的组。给出了几个以炔烃在M或M'上简单π配位为特征的例子，但大多数例子都涉及双金属活化，这与相邻的两个金属中心的协同作用有关，从而产生了双金属盐四面体，双金属环丁烯，双金属化的烯烃，多亚乙烯基和乙炔类。还涵盖了异双金属体系，其中在异二核支架的配位球中存在的两个炔配体之间或与羰基和P-给体配体之间发生了碳-碳或碳-磷偶联。此外，提出了通过将相当于C-H的R-C或相当于C-R的R-C插入末端或桥接M-H键而导致乙烯基种类的加氢金属化反应。这篇综述中还包括一些反应性研究和最初形成的杂双金属炔烃物种转化的选定实例，例如添加亲电试剂（H +，R +），生成杂金属烯基和mu-eta（1）：eta（2）-烯基盐。 （C）2017 Elsevier B.V.保留所有权利。

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