Proton-Induced Disproportionation of a Ruthenium Noninnocent Ligand Complex Yielding a Strong Oxidant and a Strong Reductant
| Autor: | Rowshan Ara Begum, Vanessa Raco, Christopher J. Dares, A. B. P. Lever, Maria Kapovsky, Elaine S. Dodsworth |
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| Rok vydání: | 2012 |
| Předmět: |
Models
Molecular chemistry.chemical_element Disproportionation Crystallography X-Ray Ligands Photochemistry Ruthenium law.invention Inorganic Chemistry law Organometallic Compounds Physical and Theoretical Chemistry Electron paramagnetic resonance Lone pair Isosbestic point Isodesmic reaction Ligand Electron Spin Resonance Spectroscopy Oxidants Crystallography chemistry Reducing Agents Quantum Theory Density functional theory Protons |
| Zdroj: | Inorganic Chemistry. 52:169-181 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic301573c |
| Popis: | The complex Ru(II)(NH(3))(2)(o-benzoquinonediimine)Cl(2) 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)](+)). 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. |
| Databáze: | OpenAIRE |
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