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Electrochemically Induced Reactivity of Ru–Arene Complexes Supported By Triarylphosphine Ligands

Year: 2026
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide 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 quasi reversible, 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(PPh 3 ) 2 (NCCH 3 ) 3 ] +, the byproduct of ET-induced reactivity of the [( p -cymene)RuCl(PPh 3 ) 2 ] + complex, indicated the cis -(PPh 3 ) 2 - fac -(CH 3 CN) 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.
DOI: 10.1021/acs.inorgchem.6c01267
Language: English
Field: Chemistry
Open Access status: hybrid
Estimated APC paid: $4,500
OpenAlex ID: W7165018131
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Cites: 87
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