NDLI: Electron transfer reactions in coordination metal complexes. Structure-reactivity relationships

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Electron transfer reactions in coordination metal complexes. Structure-reactivity relationships

Content Provider	Semantic Scholar
Author	Formosinho, Sebastitio J.
Copyright Year	1989
Abstract	- The current approach of Marcus theory to interpret electron transfer is questioned. A nother approach based on an expansion of configuration of the transition states is presented, and the r ates are estimated in terms of the following parameters: reaction energy, force constants, equilibrium bond lengths, transition state bond order and capacity to store energy. The model can interpret several anomalous features of these reactions, namely electron-exchang es where the Marcus theory e stimates rates several orders of magnitude slower and faster than experiment, "cross-relations ", solvent effects, t he i nverted region and the asymmetry of the T afel plots of metal-aquo ions, and can a ssess the nonadiabatic character of some outer-sphere processes. Electron transfer reactions play an essential role in many physical, chemical and biological processes. The investigation of the mechanisms of these reactions rests essentially on the systematic investigation of structure-reacti vity relationships that results from the geometric rearrangements which accompany the change in oxidation s tates of the coordination compounds. Although many theories have been proposed, it is no surprise that the more simpler ones such as Marcus theory are t he most popular.1 In spite of the great success of the theory of Marcus in interpreting several of these structure-reacti vity relations namely in terms of the reaction energy (AG), changes in equilibrium bond lengths (lred-lox) and metal-ligand force constants (fox and fred), several problems r emain.
Starting Page	891
Ending Page	896
Page Count	6
File Format	PDF HTM / HTML
DOI	10.1351/pac198961050891
Volume Number	61
Alternate Webpage(s)	http://media.iupac.org/publications/pac/1989/pdf/6105x0891.pdf
Alternate Webpage(s)	https://doi.org/10.1351/pac198961050891
Language	English
Access Restriction	Open
Content Type	Text
Resource Type	Article

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