Redox Equilibration Observed for the Reduction of a Ruthenium(III) Complex by Ascorbate under Low‐Driving‐Force Conditions

Abstract

A detailed kinetic study of the reduction of trans-[RuCl 2 (dipicOEt) 2 ] -, where dipicOEt = dipicolinate mono ethyl ester anion, by L-ascorbic acid that leads to the formation of the corresponding Ru II complex, was carried out spectrophotometrically using the stopped-flow technique. The reaction was studied as a function of [AscH 2 ] T and pH. The observed kinetic traces could only be fitted by a three-exponential function, characteristic of three parallel reaction paths. The complex was isolated as {[Na(H 2 O) 2 ][trans-RuCl 2 (dipicOEt) 2 ]} n , of which a single-crystal X-ray diffraction structure was determined. Detailed [a]

Characterization of a Mixed-Valence Ru(II)/Ru(III) Ion-Pair Complex. Unexpected High-Frequency Electron Paramagnetic Resonance Evidence for Ru(III)–Ru(III) Dimer Coupling

“…In the past, our mechanistic work focused on Ru­(III) picolinate (pic) and Ru­(II) polypyridyl complexes. − More recently, we initiated synthetic work to prepare complexes with mixed picolinate and polypyridyl ligands. Unfortunately, our synthetic efforts ended up in a mixture of unidentifiable complexes.…”