AbstractReactions of 2,4‐bis(4‐methoxyphenyl)‐1,3,2,4‐dithiadiphosphetane‐2,4‐disulfide with hydroxy substituted compounds (R‐OH) gave rise to the formation of dithiophosphonate compounds 2, 3 and 4 [R‐OH: N‐(2‐hydroxyethyl)‐phthalimide, 1‐(2‐hydroxyethyl)pyridine and 2‐(2‐hydroxyethyl)pyrrolidine]. Compounds 3 and 4 have been shown in zwitterionic species. The 2,4‐bis(4‐methoxyphenyl)‐1,3,2,4‐dithiadiphosphetane‐2,4‐disulfide was reacted with 2‐chloroethanol to give 4–methoxyphenyl‐2‐sulfido‐1,3,2‐oxathiaphospholane (5), synthesized by a new method. Nickel and Cadmium complexes (2a and 2c) of 1 were prepared. Compounds were characterized by elemental analysis, IR, 1H‐NMR, 31P‐NMR, UV/VIS spectroscopies and crystal structure of 5 was determined. The magnetic moment for 2b is 2.97 B.M.