Projects per year
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.
|Number of pages||2|
|Journal||Journal of the American Chemical Society|
|Early online date||12 Mar 2009|
|Publication status||Published - 8 Apr 2009|
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- 2 Finished
500 MHZ NMR SPECTROMETER TO SUPPORT ORGANIC, BIO-ORGANIC AND INORGANIC CHEMISTRY
Whittlesey, M., Danson, M., Frost, C., Kohn, R., Lowe, J., Weller, A. & Williams, J.
Engineering and Physical Sciences Research Council
12/06/06 → 11/06/09
Project: Research council