Electrochemistry and spectroelectrochemistry of oxo- and peroxomolybdenum porphyrin complexes
Journal Article
·
· Inorg. Chem.; (United States)
The electrochemistry of various oxomolybdenum(IV), -(V), and -(VI) porphyrins is reported in nonaqueous media. The investigated complexes include OMo(TPP), OMo(TPP)(X), O/sub 2/Mo(TPP), and (O/sub 2/)/sub 2/Mo(TmTP), where X = ClO/sub 4//sup -/, OCH/sub 3//sup -/, or OH/sup -/ and where TPP and TmTP are the dianions of tetraphenylporphyrin and tetra-m-tolylporphyrin, respectively. An exact sequence of the individual electron-transfer steps composing the overall redox process of each complex is described, and a comparison between the electrochemistry of the different types of complexes is discussed. Each electrode reaction was monitored by spectroelectrochemistry and by ESR spectroscopy, and on the basis of the electrochemical and spectroscopic data, a self-consistent oxidation-reduction mechanism is presented. The potential for the Mo(V)/Mo(IV) reaction of OMo(TPP)(X) is strongly influenced by the axial ligand X and varies from 0.02 V for X = ClO/sub 4//sup -/ to -0.87 V for X = OCH/sub 3//sup -/. OMo(TPP)(X) is produced by the one-electron oxidation and coupled oxygen atom transfer of O/sub 2/Mo(TPP) while OMo(TPP) is generated as the final product in the electroreduction of O/sub 2/Mo(TPP).
- Research Organization:
- Univ. of Houston, University Park, TX
- OSTI ID:
- 5108208
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 25:18; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Photoassisted reduction of molecular oxygen to hydrogen peroxide catalyzed by oxoalkoxomolybdenum(V) porphyrin
One-electron-transfer reactions of molybdenum(V) and manganese(III) porphyrins with solvated electrons and solvent radicals in 2-methyltetrahydrofuran. [Pulsed electrons; Gamma radiation]
Electrochemical studies of dimeric niobium(V) prophyrins. Reactions of ((OEP)Nb)/sub 2/O/sub 3/ and ((TpTP)Nb)/sub 2/O/sub 3/ in nonaqueous media
Journal Article
·
Wed Oct 07 00:00:00 EDT 1981
· J. Am. Chem. Soc.; (United States)
·
OSTI ID:5845270
One-electron-transfer reactions of molybdenum(V) and manganese(III) porphyrins with solvated electrons and solvent radicals in 2-methyltetrahydrofuran. [Pulsed electrons; Gamma radiation]
Journal Article
·
Tue Mar 20 23:00:00 EST 1990
· Inorganic Chemistry; (USA)
·
OSTI ID:6814229
Electrochemical studies of dimeric niobium(V) prophyrins. Reactions of ((OEP)Nb)/sub 2/O/sub 3/ and ((TpTP)Nb)/sub 2/O/sub 3/ in nonaqueous media
Journal Article
·
Wed Jun 18 00:00:00 EDT 1986
· Inorg. Chem.; (United States)
·
OSTI ID:5532359
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400400* -- Electrochemistry
ANIONS
CARBOXYLIC ACIDS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISPERSIONS
ELECTROCHEMISTRY
ELECTRODES
ELECTRON SPIN RESONANCE
ELECTRON TRANSFER
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
LIGANDS
MAGNETIC RESONANCE
MIXTURES
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPLEXES
PORPHYRINS
REDOX REACTIONS
RESONANCE
SOLUTIONS
TRANSITION ELEMENT COMPLEXES
400400* -- Electrochemistry
ANIONS
CARBOXYLIC ACIDS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DISPERSIONS
ELECTROCHEMISTRY
ELECTRODES
ELECTRON SPIN RESONANCE
ELECTRON TRANSFER
EXPERIMENTAL DATA
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
LIGANDS
MAGNETIC RESONANCE
MIXTURES
MOLYBDENUM COMPLEXES
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXYGEN COMPLEXES
PORPHYRINS
REDOX REACTIONS
RESONANCE
SOLUTIONS
TRANSITION ELEMENT COMPLEXES