[Ag(tht)(OTf)]-assisted reaction produces [AuIII(dppm)(tht)2](OSO2CF3)2, reacts with RaaiR in dichloromethane medium followed by ligand addition, and leads to [AuIII(dppm)(RaaiR)](OTf)2(RaaiR=p–R–C6H4–N=N–C3H2–NN–1–R, (1–3), abbreviated as N,N-chelator, where N(imidazole) and N(azo) represent N and N, resp.; R = H (a), Me (b), Cl (c) and R= Me (1), CH2CH3(2), CH2Ph (3), dppm is diphenylphosphinomethane, OSO2CF3 is the triflate anion, and tht is tetrahydrothiophen). Ir spectra of the complexes show –C=N– and –N=N– stretching near at 1590 and 1370 cm1 and near at 1100, 755, 695, 545, and 505 cm1 due to the presence of dppm. The H1 NMR spectral measurements suggest that methylene, –CH2–, in RaaiEt gives a complex AB type multiplet while in RaaiCH2Ph it shows AB type quartets. Electrochemistry assigns ligand reduction.