Rhodium– and iridium–perfluorophenylthiolato complexes: the X-ray structures of [(C5Me5)Ir(SC6F4H)2] and [(C5Me5)2Rh2(µ-SC6F5)3][(C5Me5)Rh(SC6F5)3] and evidence for novel equilibria in solution

Abstract

Reaction of [(C₅Me₅M)₂(µ-Cl)₂Cl₂](M = Rh, Ir) with [Pb(SR_f)₂] gave covalent [(C₅Me₅)Ir(SR_f)₂](R_f= C₆F₄H, 2b-F₄), and ionic [(C₅Me₅)₂Rh₂(µ-SR_f)₃][(C₅Me₅)Rh(SR_f)₃](R_f= C₆F₅, 2a-F₅), characterised by single crystal X-ray determinations; NMR spectra of 2b-F₄ and its analogues are compatible with a retention of the solid state structure in solution for iridium, while those of 2a-F₅ and its analogues indicate that the rhodium complexes participate in equilibria: 3[(C₅Me₅)₂Rh(SR_f)₂]⇌[(C₅Me₅)₂Rh₂(µ-SR_f)₃][(C₅Me₅)Rh(SR_f)₃].