Electrochemical and spectroelectrochemical studies of monomeric rhodium(IIII) porphyrins in nonaqueous media
The electrochemistry and spectroelectrochemistry of (TPP)Rh(NH(CH/sub 3/)/sub 2/)Cl and (TPP)Rh(NH(CH/sub 3/)/sub 2/)/sub 2//sup +/Cl/sup -/ were investigated in benzonitrile, THF, and pyridine. In benzonitrile, both of these six-coordinated Rh(III) complexes undergo two reductions and two oxidations at room temperature. No oxidations are observed in THF or pyridine (due to the limited solvent window), but two reductions are observed for the two complexes in each of these solvents. The first reduction is followed by a rapid chemical reaction, which generates a diamagnetic species that appears to be a rhodium(II) dimer. The second reduction is a two-electron reaction that produces another diamagnetic species. Electronic absorption spectra indicate the second reduction is at the porphyrin ..pi.. system. The two oxidations generate the cation radical and dication of the Rh(III) compounds and give electronic absorption and ESR spectra similar to those of other metalloporphyrin ..pi.. radical cations and dications. On the basis of the electrochemical and spectrochemical results, an overall oxidation-reduction scheme was formulated. 20 references, 11 figures, 2 tables.
- Research Organization:
- Univ. of Houston, TX
- OSTI ID:
- 5973705
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:26; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Electrochemical and spectroscopic studies of (P)Rh(R)(L) and ((P)Rh(L)/sub 2/)/sup +/ where P is the dianion of octaethyl- or tetraphenylporphyrin, R is a sigma-bonded alkyl group, and L is triphenylphosphine or dimethylphenylphosphine
Electrochemical and spectroelectrochemical studies of (TPP)(Ir(CO)/sub 3/)/sub 2/) in nonaqueous media
Related Subjects
400400* -- Electrochemistry
ABSORPTION SPECTRA
ABSORPTION SPECTROSCOPY
AROMATICS
AZINES
CARBOXYLIC ACIDS
CATIONS
CHARGED PARTICLES
CHEMICAL REACTIONS
CHEMISTRY
COMPLEXES
DATA
DIMERS
DISPERSIONS
ELECTROCHEMISTRY
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
FURANS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
IONS
LOW TEMPERATURE
MAGNETIC RESONANCE
MEDIUM TEMPERATURE
MIXTURES
MONOMERS
NITRILES
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
ORGANIC SOLVENTS
OXIDATION
PORPHYRINS
PYRIDINE
PYRIDINES
RADICALS
REDUCTION
RESONANCE
RHODIUM COMPLEXES
SOLUTIONS
SOLVENT PROPERTIES
SOLVENTS
SPECTRA
SPECTROSCOPY
TEMPERATURE DEPENDENCE
TETRAHYDROFURAN
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY