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Issue 23, 2013
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Hydrogen bonding versus hyperconjugation in condensed-phase carbocations

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Hyperconjugative stabilization of positive charge in tertiary carbocations is the textbook explanation for their stability and low frequency νCH bands in their IR spectra have long been taken as confirming evidence. While this is substantiated in the gas phase by the very close match of the IR spectrum of argon-tagged t-butyl cation with that calculated under Cs symmetry, the situation in condensed phases is much less clear. The congruence of νCHmax of t-Bu+ in superacid media (2830 cm−1) with that in the gas phase (2834 cm−1) has recently been shown to be accidental. Rather, νCHmax varies considerably as a function of counterion in a manner that reveals the presence of significant C–H⋯anion hydrogen bonding. This paper addresses the question of the relative importance of hyperconjugation versus H-bonding. We show by assigning IR spectra in the νCH region to specific C–H bonds in t-butyl cation that the low frequency νCHmax band in the IR spectrum of t-butyl cation, long taken as direct evidence for hyperconjugation, appears to be due mostly to H-bonding. The appearance of similar low frequency νCH bands in the IR spectra of secondary alkyl carboranes such as i-Pr(CHB11Cl11), which have predominant sp3 centres rather than sp2 centres (and are therefore less supportive of hyperconjugation), also suggests the dominance of H-bonding over hyperconjugation.

Graphical abstract: Hydrogen bonding versus hyperconjugation in condensed-phase carbocations

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Article information

12 Apr 2013
23 Apr 2013
First published
01 May 2013

Org. Biomol. Chem., 2013,11, 3797-3802
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Hydrogen bonding versus hyperconjugation in condensed-phase carbocations

C. A. Reed, E. S. Stoyanov and F. S. Tham, Org. Biomol. Chem., 2013, 11, 3797
DOI: 10.1039/C3OB40737C

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