Abstract
The Electrochemical behaviour of a series of cationic hydrido-complexes of Fe(II) of general formula trans-[FeH(L)(DPE) 2] (BPh 4)(L=N 2, C 2H 5N, C 6H 5CN, CH 2CHCN, CH 3CN, P(OCH 3) 3, P(OC 2H 5) 3, CO; DPE=1,2- bis(diphenylphosphino)ethane) has been investigated in 1,2-dimethoxyethane at the platinum electrode. The reduction of these d 6 complexes has been found to proceed by an ECE mechanism in which a one-electron transfer, generating a transient d 7 species, is followed by the fast loss of one of the neutral ligands and a further one-electron reduction of the pentacoordinated intermediates to the final d 8 anionic hydrides. The reduced species are stabilized considerably at low temperature. The ligands, L, are divided into two groups according to their bonding properties, with particular references to their ability to act as π- acceptors. Weak π-bonders (N 2, C 2H 5N, C 6H 5CN, CH 2CHCN, CH 3CN) are lost in the chemical step interposed between the two charge-transfer processes, whereas strong π-accepting ligands (CO and P(OR) 3) favour dissocia tion of one end of a diphosphine.
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