Non-innocent electrolyte effects on bimolecular pseudo-self-exchange reactions of ruthenium ammine complexes: Evidence for electron-transfer catalysis in H-bonded ternary assemblies

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, ( 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 -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.