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Yldiide Ligands as Building Blocks for Polynuclear Coinage Metal Complexes: Metal Squares, Triangles and Chains
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-03-26 , DOI: 10.1002/chem.202001022
Alice Johnson 1 , M. Concepción Gimeno 1
Affiliation  

Yldiides have unique electronic properties and donor abilities, but as ligands in transition metal complexes they are scarcely represented in the literature. Here, the controlled synthesis of a series of polynuclear gold yldiide complexes derived from triphenyl(cyanomethyl)phosphonium bromide, [Ph3PCH2CN]Br, under mild conditions is described. Anionic dinuclear NBu4[(AuX)2{C(CN)PPh3}] (X=Cl, C6F5) or trinuclear derivatives NBu4[Au3X2{C(CN)PPh3}] bearing terminal chloride or pentafluorophenyl groups and bridging yldiide ligands have been prepared. These compounds evolve in solution giving rise to the formation of an unprecedented tetrameric gold cluster, [Au4{C(CN)PPh3}4], by the loss of the gold complex NBu4[AuX2]. This gold cluster can also be prepared in high yield by a transmetalation reaction from the analogous tetrameric silver cluster, and two geometric isomers have been characterised, their formation dependent on the synthetic route. The triphenylphosphonium cyanomethyldiide ligand has also been used to build different dinuclear and trinuclear cationic complexes bearing phosphine or diphosphine ancillary ligands and bridging yldiide moieties. Further coordination through the cyano group of the yldiide ligand gives heterometallic trinuclear or pentanuclear derivatives. Structural characterisation of many of these compounds reveals the presence of complex molecular systems stabilised by gold⋅⋅⋅gold interactions and bridging yldiide ligands.

中文翻译:

Yldiide配体作为多核硬币金属复合物的构建基块:金属正方形,三角形和链状

乙二胺具有独特的电子性质和供体能力,但作为过渡金属络合物中的配体,它们在文献中很少出现。在此,描述了在温和条件下受控合成一系列衍生自三苯基(氰基甲基)溴化膦[Ph 3 PCH 2 CN] Br的多核金乙二胺配合物。阴离子双核NBu 4 [(AuX)2 {C(CN)PPh 3 }](X = Cl,C 6 F 5)或三核衍生物NBu 4 [Au 3 X 2 {C(CN)PPh 3}]已经制备了带有末端氯或五氟苯基和桥联乙二烯配体的基团。这些化合物在溶液中演化,通过失去金配合物NBu 4 [AuX 2 ]形成了前所未有的四聚体金簇[Au 4 {C(CN)PPh 3 } 4 ]。]。该金簇也可以通过类似的四聚体银簇的金属转移反应高产率地制备,并且已经表征了两种几何异构体,它们的形成取决于合成途径。三苯基phosph氰基甲基二酰亚胺配体也已用于构建带有膦或二膦辅助配体并桥接乙二胺部分的不同的双核和三核阳离子配合物。通过乙二基配体的氰基的进一步配位得到杂金属三核或五核衍生物。这些化合物中许多化合物的结构表征表明,存在复杂的分子系统,该系统通过金···金相互作用和架桥乙二胺配体得以稳定。
更新日期:2020-03-26
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