Abstract
The dark red octahydride complex of dirhenium, Re 2H 8(PPh 3) 4, undergoes a reversible one-electron oxidation to the blue mono-cation [Re 2H 8(PPh 3) 4] + ( E buit;1 2 −0.24 V vs. SCE by cyclic voltammetry). The X-band ESR spectrum of a dichloromethane glass (−160°C) containing the monocation is in accord with the HOMO being a delocalized metal-based orbital. Treatment of the heptahydrides ReH 7(PR 3) 2 (PR 3 = PPh 3 or PEtPh 2) with C 6H 11NC or Me 3CNC in the presence of KPF 6 leads to the elimination of hydrogen and the formation of [Re(CNR) 4(PR 3) 2]PF 6. Electrochemical oxidation of ReH 5(PPh 3) 2L (L = PPh 3, PEt 2Ph, pyridine, piperidine or cyclohexylamine) activities these molecules to attack by RNC to afford rhenium(I) species
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