The reaction of HAuCl4.4H2O with dppm(PPh2CH2PPh2) in ethanol produces [Au3(dppm)2Cl2]Cl,3. This compound equilibrates with Au2(dppm)Cl2, 1, and Au2(dppm)2 Cl2, 2, in solution. P-31 NMR studies at various temperatures suggest that the exchange rate between compounds 1 and 3 is faster than that between compounds 2 and 3. The free chloride anion in 3 is responsible for these exchanges. The strong emission of 3 in solid is attributed to the short Au ... Au distances. Crystal structure data for compound 3.EtOH : space group C2/c, with a = 14.184(3) angstrom, b = 18.556(6) angstrom, c = 20.597(6) angstrom, beta = 97.56(2)-degrees, Z = 4, and V = 5285(3) angstrom3.