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-CClF 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-CClF)] (). Its reaction with [Au(3,5-CClF)(tht)] (tht = tetrahydrothiophene) produces the gold(III) complex [Au(3,5-CClF)(tht)] (), which allows the synthesis of the diphenylohosphane derivative [Au(3,5-CClF)(PPhH)] (). Its treatment with acetylacetonate gold(I) derivatives leads to two novel Au/Au phosphanido-bridged complexes, [PPN][Au(3,5-CClF)(µ-PPh)AuCl] () and [PPN][{(3,5-CClF)Au(µ-PPh)}Au] (). All these complexes have been characterized, and the crystal structures of , , and have been established by single crystal X-ray diffraction methods, showing a novel polymeric arrangement in .