O-Tolyl/benzyl dithiocarbonates, ROCS 2 Na (R = o-, m-, or p-CH 3 C 6 H 4 -, and -CH 2 C 6 H 5 ), were synthesized and characterized. These new ligands reacted with PCl 3 /POCl 3 in refluxing toluene which resulted in the formation of phosphorus(III) and phosphorus(V) tolyl/ benzyl dithiocarbonates corresponding to [(ROCS 2 ) n PCl 3-n ] and [(ROCS 2 ) n POCl 3-n ] (R = o-, m-, or p-CH 3 C 6 H 4 -, and -CH 2 C 6 H 5 ; n = 1, 2, 3). These pale yellow liquid compounds were characterized by IR, mass, and NMR ( 1 H, 13 C, and 31 P) spectral studies, which suggest the dithiocarbonate ligands bind in a monodentate mode leading to P-S-C linkages in these derivatives.