Terminal vanadium-neopentylidyne complexes and intramolecular cross-metathesis reactions to generate azametalacyclohexatrienes.

Terminal vanadium-neopentylidyne complexes and intramolecular cross-metathesis reactions to generate azametalacyclohexatrienes. Research Abstract Details 

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Terminal vanadium-neopentylidyne complexes and intramolecular cross-metathesis reactions to generate azametalacyclohexatrienes. Abstract Text:

Falguni Basuli,Brad C Bailey,Douglas Brown,John Tomaszewski,John C Huffman,Mu-Hyun Baik,Daniel J Mindiola,

Four-coordinate vanadium complexes containing a terminal neopentylidyne functionality have been prepared by two consecutive alpha-hydrogen abstraction reactions both of which were induced by one-electron oxidations. Among these vanadium-alkylidyne complexes are the neutral and the cation (Nacnac)VCtBu(OTf) and [(Nacnac)VCtBu(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 VC bond. These alkylidynes were found to transform to azametalacyclohexatriene systems via an intramolecular cross-metathesis reaction. Kinetic studies of the transformation of (Nacnac)VCtBu(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) x 10-5 s-1 at 80 degrees C, with activation parameters DeltaH= 25.4(3) kcal/mol, DeltaS = -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 (DeltaG) in solution phase was estimated to be -21.3 kcal/mol.

Terminal vanadium-neopentylidyne complexes and intramolecular cross-metathesis reactions to generate azametalacyclohexatrienes. Publishing Authors By Initials

F Basuli,BC Bailey,D Brown,J Tomaszewski,JC Huffman,MH Baik,DJ Mindiola,

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Terminal vanadium-neopentylidyne complexes and intramolecular cross-metathesis reactions to generate azametalacyclohexatrienes. Journal Published:

PUBLICATION TYPE: Journal Article

Journal: Journal of the American Chemical Society

VOLUME: 126

Page Numbers: 10506-7

Journal Abbreviation: J. Am. Chem. Soc.

ISSN: 0002-7863

DAY: 1

MONTH: Sep

YEAR: 2004

Terminal vanadium-neopentylidyne complexes and intramolecular cross-metathesis reactions to generate azametalacyclohexatrienes. Information

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LANGUAGE: eng

NlmUniqueID: 7503056

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AFFILIATION: Department of Chemistry, School of Informatics and Molecular Structure Center, Indiana University, Bloomington, Indiana 47405, USA.

Country: United States

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MEDLINETA: J Am Chem Soc

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