RHODIUM-PERFLUOROBENZENETHIOLATO AND IRIDIUM-PERFLUOROBENZENETHIOLATO COMPLEXES, [(C5ME5)IR(SC6F5)2], [(C5ME5)IR(SC6F4H-P)2] AND [(C5ME5)2RH2(MU-SC6F5)3][(C5ME5)RH(SC6F5)3] - SYNTHESES, CRYSTAL-STRUCTURES AND SOLUTION BEHAVIOR

Reaction of [(C5Me5)2M2(mu-Cl)2Cl2] (M = Rh 1a or Ir 1b) with Pb(SRF)2 gave [(C5Me5)Ir(SRF)2] 2b (R(F) = C6F5 or C6F4H-p) containing five-co-ordinate Ir(III), or ionic [(C5Me5)2Rh2(mu-SRF)3][(C5Me5)Rh(SRF)3] 3a (R(F) = C6F5 or C6F4H-p) containing six-co-ordinate Rh(III) in both the anion and cation. Complexes 2b and 3a (R(F) = C6F5) were characterised by single-crystal X-ray determinations; the structures of 2b (R(F) = C6F5 or C6F4H-p) are very similar, but in the former the SC6F5 ligands are related by a plane of symmetry. The NMR spectra of 2b in solution are consistent with the mirror-symmetric solid-state structure. However, those of the rhodium complexes 3a, while consistent with the ionic solid-state structures in methanol, show quite different features in less-polar solvents, indicating that they participate in the equilibrium [(C5Me5)2Rh2(mu-SRF)3][(C5Me5)Rh(SRF)3] half arrow right over half arrow left 3[(C5Me5)Rh(SRF)2] where [(C5Me5)Rh(SRF)2] has a similar structure to that of 2b (R(F) = C6F5). Complexes 1a and 1b reacted with Pb(SC6H4F-p)2 to give salts formulated as the triply bridged [(C5Me5)2M2(mu-SC6H4F-p)3]Cl.H2O (M = Rh 4a or Ir 4b), while 1b reacted with Ag(SCF3) to afford the diiridium complexes [(C5Me5)2Ir2(mu-SCF3)2(SCF3)2] 5b and [(C5Me5)2Ir2(mu-SCF3)3]Cl.H2O 6b.