Synthesis and reactivity of some Group VB chalcogenide cyclo-octa-1,5-diene rhodium(I) and iridium(I) complexes

Abstract

Complexes of the type [(cod)MClL](cod = cyclo-octa-1,5-diene; M = Rh or Ir, L = Me₃PS or Me₂PhPS; M = Rh, L = Me₂PhPSe or Me₃AsS; M = Ir, L = MePh₂PS), and related cations [(cod)ML₂]⁺[M = Rh, L = Me₃PS or Me₂PhPS; M = Rh or Ir, L₂= Ph₂P(S)CH₂P(S)Ph₂] have been synthesised. The complexes [(cod)-IrClL](L = Me₃PS or Me₂PhPS) undergo oxidative-addition reactions with anhydrous HCl to give [(cod)Ir(H)-Cl₂L]. For L = Me₂PhPS a second product can be isolated, viz.[(cod)Ir(H)Cl₂]₂,C₆H₆. This is the only product for the reaction where L = MePh₂PS. The hydrido-complexes [(cod)Ir(H)Cl₂L] immediately eliminate HCl in water and ethanol. Reaction of iodine with the complexes [(cod)IrClL](L = Me₃PS or MePh₂PS) affords [(cod)IrCl(L)I₂]. The complexes have been characterised by i.r. and n.m.r. spectroscopy.