NDLI: Redox transitions of chromium, manganese, iron, cobalt and nickel protoporphyrins in aqueous solution.

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	de Groot, Matheus T. Koper, Marc T. M.
Description	Country affiliation: Netherlands Author Affiliation: de Groot MT ( Laboratory of Inorganic Chemistry and Catalysis, Schuit Institute of Catalysis, Eindhoven University of Technology, P.O. Box 513, 5600, MB Eindhoven, The Netherlands.)
Abstract	The electrochemical redox behavior of immobilized chromium, manganese, iron, cobalt, and nickel protoporphyrins IX has been investigated over the pH 0-14 range. In the investigated potential domain the metalloporphyrins were observed in four different oxidation states (M(I), M(II), M(III) and M(IV)). The metalloporphyrins differ in the potentials at which the redox transitions occur, but the observed pH dependence of the redox transitions was similar for the different metalloporphyrins and revealed that the M(II)/M(III) and M(III)/M(IV) transitions were accompanied by a hydroxide transfer at high pH. The fact that the metalloporphyrins are immobilized on graphite does not seem to have a large influence on their redox behavior, as can be deduced from the comparable behavior of immobilized metalloporphyrins on gold and of watersoluble metalloporphyrins in solution. We also performed density functional theory (DFT) calculations on the metalloporphyrins in different oxidation states. The geometries and spin states predicted by these calculations agree well with experimentally determined values; the calculations were also able to predict the electrochemical potentials of the [M(II)]/[M(III)-OH] redox transition to within about 300 mV.
File Format	HTM / HTML
ISSN	14639076
Issue Number	7
Volume Number	10
e-ISSN	14639084
Journal	Physical Chemistry Chemical Physics
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2008-02-21
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Discipline Physics Discipline Biophysics Discipline Chemistry Chromium Chemistry Cobalt Iron Manganese Nickel Protoporphyrins Computer Simulation Electrochemistry Hydrogen-ion Concentration Metalloporphyrins Molecular Structure Oxidation-reduction Photochemistry Solutions Water Journal Article Research Support, Non-u.s. Gov't
Content Type	Text
Resource Type	Article
Subject	Physics and Astronomy Physical and Theoretical Chemistry

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