Synthesis and Structural Characterization of Phosphanide Gold(III)/Gold(I) Complexes and Their Thallium(III) and Gold(III) Precursors

In this paper, we describe a series of diphenylphosphane and diphenylphosphanide gold(III) and gold(III)/gold(I) complexes containing 3,5-C₆Cl₂F₃ as aryl ligands at gold that have been synthesized due to the arylating and oxidant properties of the new polymeric thallium(III) complex [TlCl(3,5-C₆Cl₂F₃)₂]_n (1). Its reaction with [Au(3,5-C₆Cl₂F₃)(tht)] (tht = tetrahydrothiophene) produces the gold(III) complex [Au(3,5-C₆Cl₂F₃)₃(tht)] (2), which allows the synthesis of the diphenylohosphane derivative [Au(3,5-C₆Cl₂F₃)₃(PPh₂H)] (3). Its treatment with acetylacetonate gold(I) derivatives leads to two novel Au^III/Au^I phosphanido-bridged complexes, [PPN][Au(3,5-C₆Cl₂F₃)₃(µ-PPh₂)AuCl] (4) and [PPN][{(3,5-C₆Cl₂F₃)₃Au(µ-PPh₂)}₂Au] (5). All these complexes have been characterized, and the crystal structures of 1, 2, 4 and 5 have been established by single crystal X-ray diffraction methods, showing a novel polymeric arrangement in 1.