ELECTRON-TRANSFER ACTIVATION OF THE AMINOCARBYNE AND THE HYDROGEN ISOCYANIDE COMPLEXES S[RECL(CNHN)(PH(2)PCH(2)CH(2)PPH(2))(2)][BF4](N-1) (N=2 OR 1) - INTERCONVERSION OF COORDINATED CNH2 AND CNH

The aminocarbyne complex trans-[ReCl(CNH2)(dppe)(2)][BF4] (dppe = Ph(2 )PCH(2)CH(2)PPh(2)) undergoes, by cyclic voltammetry in 0.2 M [NBu(4)] [BF4]/NCMe, at a Pt electrode, a single-electron oxidation involving a nodically induced deprotonation to give the hydrogen isocyanide compou nd trans-[ReCl(CNH)(dppe)(2)](+) which exhibits, at a higher potential , a similar anodic process. Both trans-[ReCl(CNH2)(dppe)(2)][BF4] and trans-[ReCl(CNH)(dppe)(2)] can undergo proton dissociation in solution and, by cathodic reduction, dihydrogen is evolved with conceivable fo rmation of cyanide species. The mechanism of the anodic processes has been investigated by digital simulation of cyclic voltammograms which allowed the rate constants of the deprotonation reactions induced by e lectron transfer, and the acid dissociation constants for the aminocar byne species and its oxidized form, to be estimated.