Rhodium and iridium complexes with thiolate and tertiary phosphine ligands. The synthesis and structures of trans-[Ir(SC6H3Cl2-2,6)(CO)(PPh3)(2)], [Rh-2(mu-SC6H3Pr3i-2,4,6)(2)(CO)(2)-(PPh3)(2)], [Rh2H2(mu-SC6H4PPh2-2)(2)(CO)(2)(PPh3)(2)][BF4](2), and [Rh2I6(MeSC6H4PPh2-2)(2)]

Reaction of [MF(CO)(PPh3)(2)] (M=Rh or Ir) with bulky aromatic thiols ArSH gave the binuclear complexes [M-2(mu-SAr)(2)(CO)(2)(PPh3)(2)] (M=Rh, SAr=SC 6H2Pr3i-2,4,6 or SC6H3Me2-2,6) and mononuclear complexes [M(SAr)(CO)(PPh3)( 2)] (M=Rh or Ir, SAr=SC6H3Cl2-2,6 or SC6H4SiPh3-2; M=Ir, SAr=SC6H2Pr3i-2,4, 6 or SC6H3Me2-2,6. The crystal structure of [Rh-2(mu-SC6H3Pr3i-2,4,6)(2)(CO )(2)(PPh3)(2)] showed a binuclear thiolate bridged core while that of [Ir(S C6H3Cl2-2,6)(CO)(PPh3)(2)] revealed a conventional square planar geometry w ith trans PPh3 ligands. Three rhodium complexes were shown to be efficient catalysts for the hydroformylation of hept-1-ene under mild conditions with good selectivity for linear aldehyde for SAr=SC6H4SiPh3-2. Reaction of [MF (CO)(PPh3)(2)] with phosphinothiolate proligands PSH gave the monomeric com plexes [M(PS)(CO)(PPh3)(2)] (M=Rh or Ir; PS=SC6H4PPh2-2 or S(CH2)(3)PPh2; M =Rh, PS=SCH2CH2PPh2 or SCH(CH3)CH2PPh2). The complex [Rh(SC6H4PPh2-2)(CO)(P Ph3)] reacted reversibly with protons (HBF4) to give the dimeric dication [ Rh-2(mu-SC6H4PPh2-2)(2)(CO)(2)(PPh3)(2)](2+), shown by a crystal structure be a thiolate bridged dimer with an Rh-Rh bond and pseudo-octahedral geomet ry about each Rh-III. Electrophilic attack by [Me3O][BF4] on [Rh(SC6H4PPh2- 2)(CO)(PPh3)] occurred at sulfur to give [Rh(MeSC6H4PPh2-2)(CO)(PPh3)](+) a nd excess of MeI gave [Rh2I6(MeSC6H4PPh2-2)(2)], with octahedral Rh-III lin ked by a double iodide bridge. Attack at sulfur also occurred in [Rh(SC6H4P Ph2-2)(CO)(PPh3)] with I(CH2)(3)I and ICH2CO2H to give [Rh(2-Ph2PC6H4SCH2CH 2CH2)(CO)(PPh3)] and [RhI2(2-Ph2PC6H4SCH2CO2)(PPh3)] respectively. The comp lex [RhI3(CO)(PPh3)(2)] was a by-product and shown by a crystal structure t o have a pseudo-octahedral structure with trans-PPh3 ligands.