Synthesis and Characterization of New Dithiophosphonate and Ni(II) Complexes from Novel 2,4-bis(methoxytolyl)-1,3-dithia-2,4-diphosphetane 2,4-disulfides

Two new perthiophosphonic acid anhydrides, 2,4-bis(Rx,y)-1,3-dithia-2,4-diphosphetane 2,4-disulfide (Rx=3-methoxytolyle, SAV-B1 and Ry=2-methoxytolyle, SAV-B2) were synthesized. From the reaction of these dimers, (Rx,y‐P(S)S)2, with alcohols and then dry ammonia gas, ammonium salts of the dithiophosphonic acids ((Rx,y)(RnO)PS2H), Rn, R1= ethyl-, R2= 2-propyl-), namely, four new compounds of the type [NH4][S2P(Rx,y)(ORn)] were obtained. The ammonium salts were further reacted with NiCl2.6H2O to prepare four new dithiophosphonato nickel(II) complexes, [Ni(S2P(Rx,y)(ORn))]. The ligands and the complexes were characterized by mass-(ESI), 1H-, 13C-, 31P-NMR, IR-spectroscopy, HSQC techniques and elemental analyses. Complementary structural information was provided by the HSQC spectra of the [NH4][S2P(Rx,y)(OR2)]. The structure of the perthiophosphonic acid anhydrides were deduced from the structures of dithiophosphonates thereof.