Proton-induced disproportionation of a ruthenium noninnocent ligand complex yielding a strong oxidant and a strong reductant Article

Kapovsky, M, Dares, C, Dodsworth, ES et al. (2013). Proton-induced disproportionation of a ruthenium noninnocent ligand complex yielding a strong oxidant and a strong reductant . INORGANIC CHEMISTRY, 52(1), 169-181. 10.1021/ic301573c

cited authors

  • Kapovsky, M; Dares, C; Dodsworth, ES; Begum, RA; Raco, V; Lever, ABP

authors

abstract

  • The complex RuII(NH3)2(o- benzoquinonediimine)Cl2 undergoes a reversible apparent acid/base reaction, although it has no obvious basic lone pairs. The reaction is a proton-assisted disproportionation yielding an oxidant ([Ru III(NH3)2(o-benzoquinonediimine)Cl 2]+) and a reductant ([RuIII(NH 3)2(o-phenylenediamine)Cl2]+). These species were characterized by electrochemistry, ultraviolet-visible light (UV-vis), vibrational (infrared (IR) and Raman), mass and electron paramagnetic resonance (EPR) spectroscopy, and X-ray structural analysis. The reaction is shown to be downhill from an isodesmic calculation. Three different isosbestic interconversions of the parent and product species are demonstrated. The electronic structures of these species were analyzed, and their optical spectra assigned, using density functional theory (DFT) and time-dependent DFT. This disproportionation of a noninnocent ligand complex may be relevant to the application of noninnocent ligands in organometallic catalysis and in the biological milieu. © 2012 American Chemical Society.

publication date

  • January 7, 2013

published in

Digital Object Identifier (DOI)

start page

  • 169

end page

  • 181

volume

  • 52

issue

  • 1