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Lee,Jae-Duck,Villard, Anne,Kadish,Karl M.,Tabard, Alain,Souza,Francis D.,Van Caemelbecke, Eric,Guilard, Roger 東亞大學校附設基礎科學硏究所 1993 基礎科學硏究論文集 Vol.10 No.1
A self-consistent mechanism for the reduction of fluorophenyl σ-bonded iron(Ⅲ) porphyrins in noncoordinating solvents was elucidated using electrochemical and spectroelectrochemical techniques. The investigated porphyrins are represented as (P)Fe(??) and (P)Fe(??) where P is the dianion of octaethylporphyrin (OEP), tetraphenylporphyrin (TTP), terea-m-tolylporphyrin (TmTP), tetra-p-tolylporphyrin (TpTP), or tetrakis(p-(trifluoromethyl)phenyl)porphyrin (Tp-CF₃PP). Each σ-bonded compound undergoes up to seven different redox processes, some of which are associated with the initial σ-bonded complex while others are associated with the products of the initial or following electron-transfer reactions. The mechanism for reduction of(P)Fe(??) and(P)Fe(??)differs from that of all previously investigated iron porphyrins, and this is due entirely to the presence of the σ-bonded fluorophenyl ligand. The first reduction of(P)Fe(R)leads to(P)??and ??, the latter of which reacts with trace water in solution to give ??and RH. The generated ?? displaces the axial fluoropheny ligand from unreduced(P)Fe(R), and this sets in motion a chain reaction which contiunes until all of the σ-bonded porphyrin is converted to monomeric(P)FeOH prior to formation of dimeric [(P)Fe]₂O on longer time scales. The same Fe(Ⅲ) porphyrin products can also be obtained by addtion of substoichiometric amounts of ?? or ?? to(P)Fe(R), and this occurs because both anions are able to displace the fluorophenyl axial ligand from(P)Fe(R) and initiate the chain reaction in the absence of any electrochemistry.