Non-Innocent Electrolyte Effects on Bimolecular Pseudo-Self-Exchange Reactions of Ruthenium Ammine Complexes: Evidence for Electron-Transfer Catalysis in H-Bonded Ternary Assemblies – Chem.Phys., 2006, 326, 43-53.

  • 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

 “Non-Innocent Electrolyte Effects on Bimolecular Pseudo-Self-Exchange Reactions of Ruthenium Ammine Complexes: Evidence for Electron-Transfer Catalysis in H-Bonded Ternary Assemblies.” Chem.Phys., 2006, 326, 43-53.

http://www.sciencedirect.com/science/article/pii/S030101040500618X


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The kinetics of bimolecular pseudo-self-exchange reactions such as that between pentaammine(pyridine)ruthenium(II) and pentaammine(3-fluoropyridine)ruthenium(III) shown below, ( NH 3 ) 5 Ru II ( py ) 2 + + ( NH 3 ) 5 Ru III ( 3 – Fpy ) 3 + ⇄ k ex ( NH 3 ) 5 Ru III ( py ) 3 + + ( NH 3 ) 5 Ru II ( 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-muconate2− or terephthalate2− 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.

Title: Non-innocent electrolyte effects on bimolecular pseudo-self-exchange reactions of ruthenium ammine complexes: Evidence for electron-transfer catalysis in H-bonded ternary assemblies
Authors: Curtis, Jeff ChristianInagaki, MayukoChun, Sam J.Eskandari, VahidLuo, XiningPan, Zheng N.Sankararaman, UmaPengra, Gina E.Zhou, JiahuaHailey, PhilipLaurent, JeannyUtalan, Daniel
Affiliation: AA(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AB(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AC(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AD(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AE(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AF(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AG(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AH(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AI(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AJ(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AK(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States), AL(University of San francisco, 2130 fulton st., San francisco, CA 94122, United States)
Publication: Chemical Physics, Volume 326, Issue 1, p. 43-53.
Publication Date: 07/2006
Origin: ELSEVIER
Abstract Copyright: (c) 2006 Elsevier B.V.
DOI: 10.1016/j.chemphys.2005.11.035
Bibliographic Code: 2006CP….326…43C

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)+(NH3)5RuIII(3-Fpy)⇄kex(NH3)5RuIII(py)+(NH3)5RuII(3-Fpy) 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-muconate 2- or terephthalate 2- are added to the solution. The kinetic accelerations are distinct from those seen with simple electrolytes such as KCl or CaCl 2, 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.

or
The kinetics of bimolecular pseudo-self-exchange reactions such as that between pentaammine(pyridine)ruthenium(II) and pentaammine(3-fluoropyridine)ruthenium(III) shown below,

reveal a novel form of non-covalently mediated electron transfer over distance when salts of non-innocent electrolytes such as the conjugated dicarboxylic acid anionstrans,trans-muconate2− or terephthalate2− 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.

Keywords

  • Bimolecular electron transfer
  • Electron-transfer catalysis
  • Electron tunneling
  • Hydrogen bond
  • Superexchange
  • Rutheniumammine complex
  • Pseudo-self-exchange
  • Ternary association
  • Ion atmosphere
Corresponding author. Tel.: +1 415 422 6391; fax: +1 415 422 5157.

Copyright © 2005 Elsevier B.V. All rights reserved.

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