The behavior of a xanthene derivative with one bismuthane and one phosphane function, Xan(PPh₂)(BiPh₂), as a ligand toward group 11 metal cations was investigated. It was found that contact with [Cu(MeCN)₄]OTf, AgOTf, [Au(PPh₃)OTf], in all three cases leads to a transformation of Xan(PPh₂)(BiPh₂) into a tridentate PBiP system, where a BiPh unit connects two phosphinoxanthyl moieties. In the resulting compounds, [PhBi(Xan(PPh₂))₂Cu]OTf, 1, [PhBi(Xan(PPh₂))₂Ag]OTf, 2, and [PhBi(Xan(PPh₂))₂AuPPh₃]OTf, 3, the metal cations are coordinated tetrahedrally by two phosphane donors, one bismuthane donor and a fourth ligand, corresponding to OTf^– in case of 1 and 2, or PPh₃ in the case of 3. DFT calculations in combination with NBO analysis showed that the bismuth atoms in these PBiP ligands act as σ-donors. 3 thus corresponds to the first known Au^I ← Bi^III complex.

中文翻译：

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混合的磷/铋与第11组金属离子络合后PBiP配体的原位形成

研究了具有一个铋和一个膦官能团的x吨衍生物Xan（PPh ₂）（BiPh ₂）作为第11族金属阳离子的配体的行为。发现在所有三种情况下，与[Cu（MeCN）₄ ] OTf，AgOTf，[Au（PPh ₃）OTf]的接触都会导致Xan（PPh ₂）（BiPh ₂）转化为三齿PBiP系统， BiPh单元连接两个膦基黄嘌呤部分。在所得化合物中，[PhBi（Xan（PPh ₂））₂ Cu] OTf，1，[PhBi（Xan（PPh ₂））₂ Ag] OTf，2和[PhBi（Xan（PPh ₂））₂AuPPh ₃ ]光学传递函数，3，金属阳离子四面体由两个膦供体，一个供体bismuthane和第四配位体中，对应于光学传递函数的协调^-在的情况下，1和2，或PPH ₃中的情况下，3。DFT计算与NBO分析相结合显示，这些PBiP配体中的铋原子充当σ供体。因此，图3对应于第一个已知的Au ^I ←Bi ^III络合物。