309957-18-4Relevant articles and documents
Rhodium and iridium complexes with thiolate and tertiary phosphine ligands. the synthesis
Dihvorth, Jonathan R.,Morales, David,Zheng, Yifan
, p. 3007 - 3015 (2007/10/03)
Reaction of [MF(CO)(PPh3)2] (M = Rh or Ir) with bulky aromatic thiols ArSH gave the binuclear complexes [M2(u-SAr)2(CO)2(PPh3)2] (M = Rh, SAr = SC6H2Pr312,4,6 or SC6H3Me2-2,6) and mononuclear complies [M(SAr)(CO)(PPh3)J (M = Rh or Ir, SAr = SC6H3Cl2-2,6 or SC6H4SiPh3-2; M = Ir, SAr = SC6H2Prl3-2,4,6 or SC6H}Me2-2,6. The crystal structure of [Rh2(u-SC6H3Pr'3-2,4,6)2(CO) 2(PPh3)2] showed a binuclear thiolate bridged core while that of [Ir(SC6H3Cl2-2,6)(CO)(PPh3 2J revealed a conventional square planar geometry with Irans 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 complexes [M(PS)(CO)(PPh3)2] (M = Rh or Ir; PS = SC6H4PPh2-2 or S(CH2)3PPh2; M = Rh, PS = SCH2CH2PPh2 or SCH(CH3)CH2PPh2). The complex [Rh(SC6H4PPh22)(CO)(PPh3)] reacted reversibly with protons (HBF4) to give the dimeric dication [Rh2(u-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 geometry about each RhIII. Electrophilic attack by [Me3O][BF4] on [Rh(SC6H4PPh2-2)(CO)(PPh3)] occurred at sulfur to give [Rh(MeSC6H4PPh2-2)(CO)(PPh3)] + and excess of Mel gave [Rh2I6(MeSC6H4PPh2-2)2], with octahedral Rh"1 linked by a double iodide bridge. Attack at sulfur also occurred in [Rh(SC6H4PPh2-2)(CO)(PPh3)] with I(CH2)3I and ICH2CO2H to give [Rh(2-Ph2PC6H4SCH2CH2CH2)(CO)(PPh3)] and [RhI2(2-Ph2PC6H4SCH2CO2)(PPh3)] respectively. The complex [RhI3(CO)(PPh3)2] was a by-product and shown by a crystal structure to have a pseudooctahedral structure with trans-PPhj ligands. The Royal Society of Chemistry 2000.
