Gold(I) halide complexes of bis(diphenylphosphine)diphenyl ether ligands: A balance of ligand strain and non-covalent interactions

Partyka D.V.; Updegraff III J.B.; Zeller M.; Hunter A.D.; Gray T.G.

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Gold(I) halide complexes of bis(diphenylphosphine)diphenyl ether ligands: A balance of ligand strain and non-covalent interactions

机译：双（二苯基膦）二苯基醚配体的金（I）卤化物配合物：配体应变和非共价相互作用的平衡

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A series of bis(gold(i) halide; halide = Cl, Br, I) complexes of di(phosphino)diphenyl ether derivatives (L = DPEphos, DBFphos, Xantphos, tBuXantphos) have been synthesized. The new complexes have been characterized by X-ray crystallography, multinuclear NMR, and elemental analysis. The compounds luminesce at room temperature in dichloromethane solution. Many such complexes undergo aurophilic Au?Au bonding, and have chiral structures as a result. In complexes of the tBuXantphos ligand, X-ray crystallography indicates that an ion pair forms where the diphosphine ligand chelates one gold atom, and the other is part of an [AuX_2]~- counterion (X = Cl, Br, I). It appears that the observed conformations of the metal-coordinated ligands are a balance of ligand strain and non-covalent interactions, including aurophilicity, intramolecular π-stacking, halide-halide repulsion, and intramolecular Au-O interactions. Together with previous investigations, this research shows that Xantphos and its derivatives form a robust set of coordination complexes with gold that are stable in air and amenable to further synthetic manipulation. It is anticipated that these materials will be suitable precursors for gold-carbon coupling reactions and gold-based catalysis.

机译：合成了一系列的二（膦基）二苯醚衍生物（L = DPEphos，DBFphos，Xantphos，tBuXantphos）的双（金（i）卤化物;卤化物= Cl，Br，I）配合物。新的配合物已通过X射线晶体学，多核NMR和元素分析进行了表征。化合物在室温下在二氯甲烷溶液中发光。许多这样的络合物经历亲金的Au 2 Au键，结果具有手性结构。在tBuXantphos配体的络合物中，X射线晶体学表明形成了一个离子对，其中二膦配体螯合一个金原子，另一个是[AuX_2]-抗衡离子的一部分（X = Cl，Br，I）。似乎观察到的金属配位配体的构型是配体应变和非共价相互作用的平衡，包括亲酸性，分子内π堆积，卤化物-卤化物排斥和分子内Au-O相互作用。与以前的研究一起，这项研究表明Xantphos及其衍生物与金形成了一套稳固的配位络合物，它们在空气中稳定并且可以进行进一步的合成处理。预计这些材料将是用于金-碳偶联反应和金基催化的合适前体。

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《Dalton transactions: An international journal of inorganic chemistry》 |2010年第22期|共10页
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Partyka D.V.; Updegraff III J.B.; Zeller M.; Hunter A.D.; Gray T.G.;
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Gold(I) halide complexes of bis(diphenylphosphine)diphenyl ether ligands: A balance of ligand strain and non-covalent interactions

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