Terminal Vanadium−Neopentylidyne Complexes and Intramolecular Cross-Metathesis Reactions to Generate Azametalacyclohexatrienes
- 5 August 2004
- journal article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (34), 10506-10507
- https://doi.org/10.1021/ja0472376
Abstract
Four-coordinate vanadium complexes containing a terminal neopentylidyne functionality have been prepared by two consecutive α-hydrogen abstraction reactions both of which were induced by one-electron oxidations. Among these vanadium−alkylidyne complexes are the neutral and the cation (Nacnac)V⋮CtBu(OTf) and [(Nacnac)V⋮CtBu(THF)]+, respectively (Nacnac- = [Ar]NC(CH3)CHC(CH3)N[Ar], Ar = 2,6-(CHMe2)2C6H3). The vanadium−alkylidynes have been characterized by 1H, 13C, 51V NMR spectroscopy and single-crystal X-ray diffraction and are consistent with a short V⋮C bond. These alkylidynes were found to transform to azametalacyclohexatriene systems via an intramolecular cross-metathesis reaction. Kinetic studies of the transformation of (Nacnac)V⋮CtBu(OTf) in C7D8 reveal the formation of the azametalacyclohexatriene to be independent of solvent (toluene vs THF) and the reaction to be first order in vanadium (k = 3.30(5) × 10-5 s-1 at 80 °C, with activation parameters ΔH⧧= 25.4(3) kcal/mol, ΔS⧧ = −6(3) cal/molK). High-level DFT calculations on the full model suggest an intramolecular mechanism invoking only one transition state. The overall thermodynamic driving force for the reaction (ΔG) in solution phase was estimated to be −21.3 kcal/mol.Keywords
This publication has 10 references indexed in Scilit:
- Cationic and Neutral Four‐Coordinate Alkylidene Complexes of Vanadium(IV) Containing Short VC BondsAngewandte Chemie-International Edition, 2004
- High Oxidation State Multiple Metal−Carbon BondsChemical Reviews, 2001
- Carbon-Carbon and Carbon-Heteroatom Coupling Reactions of MetallacarbynesChemical Reviews, 1995
- Vanadium-promoted reductive coupling of carbon monoxide and facile hydrogenation to form cis-disiloxyethylenesJournal of the American Chemical Society, 1991
- High-oxidation-state molybdenum and tungsten alkylidyne complexesAccounts of Chemical Research, 1986
- Multiple metal carbon bonds. 35. A general route to tri-tert-butoxytungsten alkylidyne complexes. Scission of acetylenes by ditungsten hexa-tert-butoxideOrganometallics, 1985
- Tungsten(VI) neopentylidyne complexesOrganometallics, 1982
- Metathesis of tungsten-tungsten triple bonds with acetylenes and nitriles to give alkylidyne and nitrido complexesJournal of the American Chemical Society, 1982
- Tantalum-neopentylidene hydride and tantalum-neopentylidyne hydride complexesJournal of the American Chemical Society, 1980
- The tungsten-tungsten triple bond. 8. Dinuclear alkoxides of tungsten(III) and structural characterization of hexaisopropoxybis(pyridine)ditungsten, the first compound with four-coordinated tungsten atoms united by a triple bondInorganic Chemistry, 1979