Substituted Bisphosphanylamines as Ligands in Gold(I) Chemistry – Synthesis and Structures

Abstract Dimethyl 5‐aminoisophthalate, which is a building block of amino‐substituted tetralactam macrocycles, was used as ligand in gold(I) chemistry to form model complexes for macrocyclic gold compounds. Reaction of dimethyl 5‐aminoisophthalate with chlorodiphenylphosphine gave the diphosphine compound dimethyl 5‐[N,N‐bis(diphenylphosphanyl)amino]isophthalate (dmbpaip). This compound can further be reacted with [AuCl(tht)] (tht = tetrahydrothiophene) to give the dinuclear complex [Au2Cl2(dmbpaip)]. In contrast, treatment of dmbpaip with [Au(tht)2]ClO4 resulted in the ionic compound [Au2(dmbpaip)2](ClO4)2 in which the cation forms an eight‐membered Au2P4N2 heterocycle. In both gold(I) compounds Au···Au interactions are observed. All new compounds were characterized by single‐crystal X‐ray diffraction.