Multinuclear Pd and Pt complexes with bridging Si- and Ge-ligands. Stable and flexible coordination bonds and structures and reactions of the molecules
Multinuclear Pd and Pt complexes with bridging Si- and Ge-ligands. Stable and flexible coordination bonds and structures and reactions of the molecules
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具有桥接 Si 和 Ge 配体的多核 Pd 和 Pt 配合物。
DOI：
10.1016/j.ccr.2020.213195
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发表时间：
2020
影响因子：
20.6
通讯作者：
Makoto Tanabe
中科院分区：
文献类型：
--
作者：
Kohtaro Osakada;Yoshitaka Tsuchido;Makoto Tanabe
金属-硅或金属-锗配合物表现出金属-碳配合物所没有的化学性质。本文综述了近几十年来关于具有桥接Si-和Ge-配体的多核基团10过渡金属配合物的报道。对桥接Si-和Ge-配体的双钯和双铂配合物的研究揭示了配体的sissingle -键h和gessingle -键h键的活化以及氢化物与桥接Si-和Ge-配体的反成键反应。部分配合物在温和条件下发生分子内sisingingsi和gesingingdge成键反应。三角形三铂(0)配合物具有三个桥接二芳基硅烯配体，在添加炔后引起骨架重排。含H2SiPh2配体的配合物可以催化芳香醛和酮的硅氢化反应。四核、五核、六核和八核Pd和Pt配合物与桥接硅烯和锗烯配体通过单核和双核金属配合物与Si和Ge配体的热反应得到。将CuI和AgI加入Pd和Pt的平面四核配合物中，使配合物具有pd单键Pd（Pt）单键cu （Ag）三角形，而加热产物使CuI和AgI消除，使四核平面配合物再生。
Late transition metal complexes with metal-silicon or metal-germanium σsingle bondbond show the chemical properties that could not be found for the complexes with metal-carbon σsingle bondbond. In this article, we review reports on the multinuclear group 10 transition metal complexes having bridging Si- and Ge- ligands for these several decades. Studies of dipalladium and diplatinum complexes with bridging Si- and Ge- ligands revealed activation of the Sisingle bondH and Gesingle bondH bonds of the ligands as well as the reverse bond-forming reactions of hydride and bridging Si- and Ge- ligands. A part of the complexes undergo intramolecular Sisingle bondSi and Gesingle bondGe bond forming reactions under mild conditions. Triangular triplatinum(0) complexes having three bridging diarylsilylene ligands cause skeletal rearrangement upon addition of alkynes. The complex with SiPh2ligands catalyzes the hydrosilylation of aromatic aldehydes and ketones with H2SiPh2. Tetra-, penta-, hexa-, and octanuclear Pd and Pt complexes with bridging silylene and germylene ligands are obtained from thermal reactions of the mono- and di-nuclear metal complexes with Si- and Ge- ligands. Addition of CuI and AgI to the planar tetranulcelar complexes of Pd and Pt affords the complexes having a Pdsingle bondPd(Pt)single bondCu(Ag) triangle, while heating the product causes elimination of CuI and AgI and regeneration of the tetranuclear planar complex.