Structure and Dynamics of Tetrakis(thiophosphinato)resorcinarene Complexes of Silver(I), Gold(I), and Palladium(II)

The coordination chemistry of the tetrakis(thiophosphinato)resorcinarene sulfur-donor ligands [(C6H2CH{CH2CH2Ph})4{OC(O)R}4{OP(S)Ph2}4] (L), where R = OCH2Ph, 4-C6H4CH3, C6H11, C4H3S, or OCH2CCH, is reported. Both silver(I) and gold(I) form cationic complexes of the type [LM2]2+, in which the ligand acts as a bis(chelate) in forming complexes with linear S−M−S (M = Ag or Au) stereochemistry. Gold(I) also forms the unusual complex [L(AuCl)2][LAu2]2+, which forms a supramolecular polymer through intermolecular aurophilic attractions. Palladium(II) forms the complex [LPd2Cl2(μ-Cl)2], in which the dipalladium(II) unit extends the natural bowl structure of the resorcinarene. The solid-state and solution conformations of the complexes, as determined by X-ray structure determination and NMR spectroscopy, respectively, are similar, but several complexes were found to exhibit dynamic behavior in solution, involving either conformational mobility of the resorcinarene unit or intermolecular ligand exchange.