Publication: Proton induced Disproportionation of a Ruthenium Non-innocent Ligand Complex yielding a Strong Oxidant and a Strong Reductant

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Title	Proton induced Disproportionation of a Ruthenium Non-innocent Ligand Complex yielding a Strong Oxidant and a Strong Reductant
Authors/Editors*	M. Kapovsky, C. Dares, E. Dodsworth, R. Begum, V. Raco, and A. B. P. Lever
Where published*	Inorganic Chemistry
How published*	Journal
Year*	2013
Volume	52
Number	1
Pages	169-81
Publisher	ACS
Keywords	non-innocent ligand, DFT
Link	DOI: 10.1021/ic301573c
Abstract	The complex Ru II (NH 3 ) 2 (o-benzoquinonediimine)Cl 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 (NH 3 ) 2 (o-benzoquinonediimine)Cl 2 ] + ) and a reductant ([Ru III (NH 3 ) 2 (o-phenylenediamine)Cl 2 ] + 2 ). These species were characterized by electrochemistry, ultravioletâvisible 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 diï¬erent 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.