The complexes LAuCl 3 [L = 1-phenyl-3,4-dimethylphosphole(DMPP), 1- phenyldibenzophosphole(DBP) and triphenylphosphine], LAuBr 3 (L = DBP, Ph 3P) and LAuClBr 2 (L = DBP, Ph 3P) were prepared and characterized by physical properties, cyclic voltammetry, far IR, 31P { 1H} and CP/MAS 31P{ 1H} NMR spectroscopy. Ligand redistribution, reactions of the types: LAuCl + L′AuBr ⇌L′AuCl + LAuBr; LAuCl 3 + LAuBr 3⇌ LAuCl n Br 3− n ; LAuCl 3 + L′AuBr 3⇌ LAuCl n Br 3− n +L′AuCl n Br 3− n ; and LAu Cl+L′AuBr 3⇌ LAuBr+L′AuCl+L′AuBr+LAuCl n Br 3− n +L′AuCl n Br 3− n all occur rapidly and have been studied by 31P{ 1H} NMR spectroscopy. These reactions all appear to proceed by way of halide-bridged intermediates. The solid state identities of LAuClBr 2 were established by a combination of far IR and CP/MAS 31P{ 1H} NMR spectroscopies and single crystal X-ray crystallography for Ph 3PAuBr 2Cl. The R 3PAuBr 2Cl complexes are substitutionally disordered, probably with two-thirds bromine and one-third chlorine in each site. Ph 3PAuBr 2Cl crystallized in the monoclinic space group P2 1/c with a = 9.086(2), b = 11.410(2), c = 18.734(4) Å, β = 95.01°(2), and Z = 4. The structure was solved by least-squares methods with R F = 0.074 for 1919 unique reflections with I/σ( I) $ ̄ 3.0. The gold atom has nearly regular square-planar coordination with AuP = 2.314(6) A° and AuX = 2.399(3), 2.413(3) and 2.415(4) Å°.