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Publication Type
Journal Article
UWI Author(s)
Author, Analytic
Bakir, Mohammed, A.; McKenzie, J.
Author Affiliation, Ana.
Chemistry; Faculty of Pure and Applied Sciences
Article Title
Electrochemical reactions of CO2 with fac-Re(dpk)(CO)3Cl (dpk=di-2-pyridyl ketone)
Medium Designator
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Connective Phrase
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Journal Title
Journal of Electroanalytical Chemistry
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Reprint Status
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Date of Publication
1997
Volume ID
425
Issue ID
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Page(s)
61-66
Language
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Connective Phrase
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Location/URL
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ISSN
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Notes
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Abstract
The electrochemical reactions between CO2 and fac-Re(dpk)(CO)3Cl (1) are solvent dependent, controlled by the rate of diffusion of electroactive species from the electrode surface. Fast diffusion due to solvent or scan rate variations inhibits the carboxylation of the carbonylic carbon atom of the radical anion fac-Re{(C5H4N)2(CO)-}(CO)3Cl (II) and leads to the generation of a coordinatively unsaturated fac-Re[(C5H4N)2{(CO)-}(CO)3 (VIII) that binds CO2 at the metal center to form fac-Re[(C5H4N)2{(CO)-}](CO3)](CO2) (IX). Slow diffusion facilitates the carboxylation of the carbonylic carbon atom of II to form fac-Re[(C5H4N)2{C(O-)(CO2)](CO)3 (III) that undergoes a second electronic transfer followed by chemical steps leading to the formation of fac-Re[C5H4N)2{C(O)(CO2H)}](CO)3 (VI)....
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