Unusual hydrogen transfer pathways in a Re–Pt heterobimetallic system

Abstract

The cation cis-[cp(OC)(ON)Re(µ-Pcy₂)PtH(PPh₃)₂]⁺{obtained from the oxidative addition of [cp(OC)(ON)RePcy₂H]⁺ to Pt(C₂H₄)(PPh₃)₂; cp = cyclopentadienyl, cy = cyclohexyl}, undergoes a base-catalysed proton transfer accompanied by Co loss to give a terminal rhenium–hydrido cation [cp(ON)H[graphic omitted](PPh₃)₂]⁺ as the kinetically formed product, which in the presence of halide ions (other than F^–) isomerizes to the thermodynamically preferred product [cp(ON)Re(µ-Pcy₂)(µ-H)Pt(PPh₃)₂]⁺.