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Can Electrophilicity Act as a Measure of the Redox Potential of First‐Row Transition Metal Ions?
Author(s) -
Moens Jan,
Roos Goedele,
Jaque Pablo,
De Proft Frank,
Geerlings Paul
Publication year - 2007
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.200700547
Subject(s) - electrophile , redox , solvation , chemistry , density functional theory , computational chemistry , chemical physics , transition metal , implicit solvation , ion , metal ions in aqueous solution , inorganic chemistry , catalysis , organic chemistry
Previous contributions concerning the computational approach to redox chemistry have made use of thermodynamic cycles and Car–Parrinello molecular dynamics simulations to obtain accurate redox potential values, whereas this article adopts a conceptual density functional theory (DFT) approach. Conceptual DFT descriptors have found widespread use in the study of thermodynamic and kinetic aspects of a variety of organic and inorganic reactions. However, redox reactions have not received much attention until now. In this contribution, we prove the usefulness of global and local electrophilicity descriptors for the prediction of the redox characteristics of first row transition metal ions (from Sc 3+ |Sc 2+ to Cu 3+ |Cu 2+ ) and introduce a scaled definition of the electrophilicity based on the number of electrons an electrophile ideally accepts. This scaled electrophilicity concept acts as a good quantitative estimate of the redox potential. We also identify the first solvation sphere together with the metal ion as the primary active region during the electron uptake process, whereas the second solvation sphere functions as a non‐reactive continuum region.