The reaction of 2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide (Lawesson''s Reagent, LR) with NiCl2 or Co(CH3COO)2 in methanol or ethanol gives novel sulfur-rich complexes: C16H20NiO4P2S4 (1), C18H24NiO4P2S4 (2) and C24H30CoO6P3S6 (4). With the presence of ethylenediamine under the same conditions, complex C24H48N6NiO4P2S4 (3) is also obtained. These four novel sulfur-rich complexes were characterized by IR and X-ray crystallography, which indicate that the solvent can influence the crystal structure of complexes in the reaction between LR and metal. [Copyright &y& Elsevier]