Proton-Induced Disproportionation of a Ruthenium Noninnocent Ligand Complex Yielding a Strong Oxidant and a Strong Reductant

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 ([RuIII(NH3)2(o-benzoquinonediimine)Cl2]+) and a reductant ([RuIII(NH3)2(o-phenyl...

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Bibliographic Details
Published in:Inorganic chemistry 2013-01, Vol.52 (1), p.169-181
Main Authors: Kapovsky, Maria, Dares, Christopher, Dodsworth, Elaine S, Begum, Rowshan Ara, Raco, Vanessa, Lever, A. B. P
Format: Article
Language:English
Subjects:
Crystallography, X-Ray
Electron Spin Resonance Spectroscopy
Ligands
Models, Molecular
Organometallic Compounds - chemical synthesis
Organometallic Compounds - chemistry
Oxidants - chemical synthesis
Oxidants - chemistry
Protons
Quantum Theory
Reducing Agents - chemical synthesis
Reducing Agents - chemistry
Ruthenium - chemistry
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Summary: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 ([RuIII(NH3)2(o-benzoquinonediimine)Cl2]+) and a reductant ([RuIII(NH3)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.
ISSN:0020-1669
1520-510X
DOI:10.1021/ic301573c