VOLTAMMETRY OF OXORHENIUM(V) COMPLEXES CONTAINING THE [O = RE-OR] CORE AND SUBSTITUTED PYRIDINE LIGANDS

Compounds of the general formula [ORe(OR)Cl2(PPh3)2] and [ORe(OEt)Cl2(PPh3)(py)], where R = alkyl or aryl and py = a substituted pyridine, were synthesized and their voltammetric behaviour investigated. For the former, the electron-transfer mechanism was observed to be dependent on solvent. In dry MeCN, a quasi-reversible oxidation and a reduction followed by a chemical reaction was observed. There were indications of nucleophilic attack on electrochemically generated [ORe(OEt)Cl2(PPh3)2]+, forming an unstable species whose reduction potentials were strongly dependent on the identity of the nucleophile. Voltammetric and spectroscopic observations of the oxorhenium(V) alkoxypyridine complex indicate the pyridine to be labile in halogenated hydrocarbon solvents but not in Me2CO, MeCN, or CCl4. Electrochemical generation of [ORe(OEt)Cl2(PPh3)(ClxCyHz)]+ (x = 1,2, or 3; y = 1 or 2; z = 2,3, or 4) appears to be followed by transfer of a hydrogen atom from the solvent to form [(HO)Re(OEt)Cl2(PPh3)]+. Various pyridine complexes of this type were prepared via substitution reactions under mild conditions. Varying the reaction conditions allowed the synthesis of trans-dioxotetrapyridyl complexes in excellent yield.