114466-58-9Relevant academic research and scientific papers
Electrochemistry of vanadyl porphyrins in dimethylformamide
Kadish,Sazou,Araullo,Liu,Saoiabi,Ferhat,Guilard
, p. 2313 - 2320 (2008/10/08)
The electrochemistry of (P)VO in DMF is reported where P is the dianion of tetrapyridylporphyrin (TpyP), tetrakis(p-sulfonatophenyl)porphyrin (T(p-SO3Na)PP), or tetrakis(p-(diethylamino)phenyl)porphyrin (T(p-Et2N)PP). (TpyP)VO and (T(p-SO3Na)PP)VO are able to bind a sixth axial ligand, and values of formation constants for DMF addition to [(P)VO]- and (P)VO in CH2Cl2 were calculated by using electrochemical and spectral methods. The [T(p-Et2N)PP]VO complex does not axially bind DMF. Electrode reactions of the three vanadyl complexes were monitored in DMF by cyclic voltammetry, rotating-disk voltammetry, and spectroelectrochemistry. Each complex is reduced in two one-electron-transfer steps to give a π anion radical and a dianion. [T(p-SO3Na)PP]VO and [T(p-Et2N)PP]VO undergo several oxidations in DMF, but (TpyP)VO is not oxidized within the potential range of the solvent. The first one-electron abstraction from [T(p-SO3Na)PP]VO and [T(p-Et2N)PP]VO generates a porphyrin π cation radical while subsequent oxidations involve reactions of DMF or one of the diethylamino groups for the case of [T(p-Et2N)PP]VO. The effect of porphyrin ring structure on the redox reactions and electrode mechanisms of each complex in DMF is discussed.
