THE CHEMISTRY OF HETERO-ALLENE AND -ALLYLIC DERIVATIVES WITH RHODIUM AND IRIDIUM. III. ELIMINATION OF HETERO-ALLENE MOLECULES FROM RHODIUM(I)-HETERO-ALLYLIC-PHOSPHINE COMPLEXES. THE FIRST COMPLEX WITH η2-COORDINATED Ph2PS-

Article abstract of DOI:10.1016/S0022-328X(00)93337-0

Carbon monoxide causes elimination of the hetero-allene molecules ptolN=C=Nptol and Ph-N=C=O in Rh(PPh3)2 and Rh(PPh3)2, respectively.The resulting complex in both cases is n.In the reaction of RhCl(PPh3)3 with Ph2P(S)C(Nptol)NHptol or Ph2P(S)C(O)NHPh in the presence of a base, a similar elimination occurs yielding the liberated heterocumulene and Rh(PPh3)2(SPPh2).This complex is the first example of a species with a side-on coordinated PH2PS-moiety.We have also prepared this compound and other species, containing η²-SPPh2, via direct interaction of RhCl(PPh3)3 and IrCl(PPh3)2(C8H14) with Ph2P(S)H.Upon reaction with CO, the chelating PPh2 group is displaced by CO to give complexes with and end-on coordinated Ph2PS^- ligand.Finally, Rh(PPh3)2(SPPh2) incorporates three moles of PhNCS, one by insertion and two by disproportionation, to yield Rh(PPh3)(PhNC)(PhNCS2).