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Updated: Jun 19, 2026

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
Published on: April 10, 2015
Electrochemically Induced Reactivity of Ru-Arene Complexes Supported By Triarylphosphine Ligands
Julia E Fumo1, Anthony N Micci1, Christopher Yang1
1Department of Chemistry, Franklin & Marshall College, P.O. Box 3003, Lancaster, Pennsylvania 17604, United States.
Abstract:
Half-sandwich ruthenium(II) complexes supported by phosphine ligands typically undergo one-electron oxidation processes at potentials that depend on the identity of the phosphine ligand. While in noncoordinating solvents these electron transfer (ET) processes are often quasireversible, electrochemical oxidation in the presence of exogenous ligands (such as in coordinating solvents) results in chemical reactivity of the nascent Ru(III) species. Herein, we report the synthesis and spectroscopic, structural, and electrochemical characterization of several series of (p-cymene)Ru complexes, including dichloride, solvento, bis(phosphine), and benzonitrile compounds. Based on extensive comparisons across these series of complexes and of Hammett analyses of the effects of phosphine-based substituents on Ru reduction potential, this ET-induced reactivity was confirmed to involve dissociation of the cymene moiety and incorporation of three nitrile ligands, with retention of the phosphine and chloride ligands present in the relative precursors. Investigations into the properties of the three isomers of [RuCl(PPh3)2(NCCH3)3]+, the byproduct of ET-induced reactivity of the [(p-cymene)RuCl(PPh3)2]+ complex, indicated the cis-(PPh3)2-fac-(CH3CN)3 isomer as the likely form of the complex generated following electrochemical oxidation, suggesting that ET-induced ligand exchange results in replacement of the facially coordinated arene ligand with three monodentate ligands also in a facial arrangement.
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