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A Well-Defined Terminal Vanadium(III) Oxo Complex

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Atanasov,  Mihail
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;
Institute of General and Inorganic Chemistry, Bulgarian Academy of Sciences;

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Bill,  Eckhard
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

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Citation

King, A. E., Nippe, M., Atanasov, M., Chantarojsiri, T., Wray, C. A., Bill, E., et al. (2014). A Well-Defined Terminal Vanadium(III) Oxo Complex. Inorganic Chemistry, 53(21), 11388-11395. doi:10.1021/ic5010177.


Cite as: http://hdl.handle.net/21.11116/0000-0007-A244-5
Abstract
The ubiquity of vanadium oxo complexes in the V+ and IV+ oxidation states has contributed to a comprehensive understanding of their electronic structure and reactivity. However, despite being predicted to be stable by ligand-field theory, the isolation and characterization of a well-defined terminal mononuclear vanadium(III) oxo complex has remained elusive. We present the synthesis and characterization of a unique terminal mononuclear vanadium(III) oxo species supported by the pentadentate polypyridyl ligand 2,6-bis[1,1-bis(2-pyridyl)ethyl]pyridine (PY5Me2). Exposure of [VII(NCCH3)(PY5Me2)]2+ (1) to either dioxygen or selected O-atom-transfer reagents yields [VIV(O)(PY5Me2)]2+ (2). The metal-centered one-electron reduction of this vanadium(IV) oxo complex furnishes a stable, diamagnetic [VIII(O)(PY5Me2)]+ (3) species. The vanadium(III) oxo species is unreactive toward H- and O-atom transfer but readily reacts with protons to form a putative vanadium hydroxo complex. Computational results predict that further one-electron reduction of the vanadium(III) oxo species will result in ligand-based reduction, even though pyridine is generally considered to be a poor π-accepting ligand. These results have implications for future efforts toward low-valent vanadyl chemistry, particularly with regard to the isolation and study of formal vanadium(II) oxo species.