Article ID | Journal | Published Year | Pages | File Type |
---|---|---|---|---|
5376941 | Chemical Physics | 2006 | 11 Pages |
Abstract
The kinetics of bimolecular pseudo-self-exchange reactions such as that between pentaammine(pyridine)ruthenium(II) and pentaammine(3-fluoropyridine)ruthenium(III) shown below,(NH3)5RuII(py)2++(NH3)5RuIII(3-Fpy)3+âkex(NH3)5RuIII(py)3++(NH3)5RuII(3-Fpy)2+reveal a novel form of non-covalently mediated electron transfer over distance when salts of non-innocent electrolytes such as the conjugated dicarboxylic acid anions trans,trans-muconate2â or terephthalate2â are added to the solution. The kinetic accelerations are distinct from those seen with simple electrolytes such as KCl or CaCl2, and are thus outside the realm of classical electrolyte effects described by the Debye-Huckel theory of ion atmospheres. Kinetic simulations are presented, and the rate acceleration is interpreted in the context of possible superexchange-type interactions taking place in hydrogen-bonded ternary (or higher) association complexes which create new kinetic pathways for electron transfer over distance in aqueous solution.
Related Topics
Physical Sciences and Engineering
Chemistry
Physical and Theoretical Chemistry
Authors
Jeff Christian Curtis, Mayuko Inagaki, Sam J. Chun, Vahid Eskandari, Xining Luo, Zheng N. Pan, Uma Sankararaman, Gina E. Pengra, Jiahua Zhou, Philip Hailey, Jeanny Laurent, Daniel Utalan,