Reduction of copper tetracyanotetraphenylporphyrin in nonaqueous media. Formation of copper(I)
- Universite Louis Pasteur, Strasbourg, France
The total electrochemical reduction of copper tetracyanotetraphenylporphyrin, (CN)/sub 4/(TPP)Cu, was investigated in dimethylformamide (DMF) by the techniques of polarography cyclic voltammetry, thin-layer spectroelectrochemistry, ESR spectroscopy, and extended Huckel calculations. The ESR results establish the existence of a Cu(II) dianion. The electrochemical reactions of (TPP)Cu and (CN)/sub 4/(TPP)Cu are compared, and the differences in redox behavior can be rationalized by the calculations. Unlike (TPP)Cu, which may be reduced by a total of six electrons in four steps, (CN)/sub 4/(TPP)Cu is reduced by seven electrons in five steps. This new wave occurs at E/sub 1///sub 2/ = -1.95 V in DMF and is attributed to reduction of the Cu(II) dianion to yield a Cu(I) complex. Formation of this species is reversible on the cyclic voltammetry time scale and an electronic spectrum has been obtained. This spectrum consists of a split Soret band at 390.0 and 480.4 nm and a strong band in the visible at 688.2 nm.
- OSTI ID:
- 5225591
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 21:4; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
400102 -- Chemical & Spectral Procedures
400400* -- Electrochemistry
AMIDES
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
COMPLEXES
COPPER COMPLEXES
DATA
ELECTRON TRANSFER
ENERGY LEVELS
EXPERIMENTAL DATA
FORMAMIDE
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PORPHYRINS
REDOX POTENTIAL
REDOX REACTIONS
REDUCTION
SPECTRA
TRANSITION ELEMENT COMPLEXES