A digold(I) complex, [Au-2(D-Hpen-S)(2)(dppm)] ([1]), newly prepared from [Au2Cl2(dppm)] and D-H(2)pen, readily reacted with Ni2+ to give a S-bridged (NiAu2I)-Au-II trinuclear complex having an 8-membered chelating metalloring, [Au-2(dppm){Ni(D-pen-N,O,S)(2)}] ([2]). Complex [2] was reversibly converted to a (NiAu3I)-Au-II tetranuclear complex having a 12-membered metalloring, [Au-3(dppm)(2){Ni(D-pen-N,O,S)(2)}]Cl ([3]Cl), retaining the coordination environment about a Ni-II center.