Reaction of the mononuclear nickel-thiolate complex [Ni(L1)(dppe)] with CH2Cl2 affords the novel pentanuclear complex [Ni5Cl2(L1)4(dppe)2], while [Ni(L1)(dcpe)] reacts with CH2Cl2 to give the binuclear species [Ni2Cl2(L2)(dcpe)2] in which two L1 units are linked by a methylene group derived from CH2Cl2.