Activation of an alkyl C-H bond geminal to an agostic interaction: an unusual mode of base-induced C-H activation
Haller, L. J. L., Page, M. J., Macgregor, S. A., Mahon, M. F. and Whittlesey, M. K., 2009. Activation of an alkyl C-H bond geminal to an agostic interaction: an unusual mode of base-induced C-H activation. Journal of the American Chemical Society, 131 (13), pp. 4604-4605.
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Deuterium labeling studies indicate that base-induced intramolecular C−H activation in the agostic complex 2-D proceeds with exclusive removal of a proton from the methyl arm of an iPr substituent on the N-heterocyclic carbene (NHC) ligand. Computational studies show that this alkyl C−H bond activation reaction involves deprotonation of one of the C−H bonds that is geminal to the agostic interaction, rather than the agostic C−H bond itself. The reaction is readily accessible at room temperature, and a computed activation barrier of ΔE ‡calcd = +11.8 kcal/mol is found when the NHC 1,3-diisopropyl-4,5-dimethylimidazol-2-ylidene is employed as the external base. Charge analysis reveals that the geminal hydrogens are in fact more acidic than the agostic proton, consistent with their more facile deprotonation.
|Creators||Haller, L. J. L., Page, M. J., Macgregor, S. A., Mahon, M. F. and Whittlesey, M. K.|
|Departments||Faculty of Science > Chemistry|
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