Abstract The homoleptic gold (I) thiolates of formula [Au (SR)] n (R= CMe 3, CH 2 CMe 3, CH 2 CHMe 2, CPh 3) have been converted into their phosphane derivatives of general formula [Au (SR)(L)](L= PMe 3, PMe 2 Ph, PMePh 2, PPh 3) and [Au 2 (SR) 2 (dppe)][dppe= 1, 2-bis (diphenylphosphanyl) ethane], which have been characterized by elemental analysis, mass spectrometry, 1 H and 31 P NMR spectroscopy and cyclic voltammetry. Complexes [Au ( ...