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J Phys Chem A. 2015 Aug 13;119(32):8619-29. doi: 10.1021/acs.jpca.5b04657. Epub 2015 Jul 29.

tert-Butyl Carbocation in Condensed Phases: Stabilization via Hyperconjugation, Polarization, and Hydrogen Bonding.

Author information

1
†N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry, Siberian Branch of the Russian Academy of the Sciences (SB RAS), Novosibirsk 630090, Russia.
2
‡Department of Natural Science, National Research University - Novosibirsk State University, Novosibirsk 630090, Russia.
3
§Department of Chemistry and Biochemistry, Florida State University, Tallahassee, Florida 32306, United States.

Abstract

Despite the seeming similarity of the infrared (IR) spectra between tert-butyl cations (t-Bu(+)) in gaseous and condensed phases, there are important but so far unrecognized differences. The IR spectroscopic investigation of the hydrogen (H)-bonding of t-Bu(+) with the immediate environment together with the X-ray crystallographic data shows that one CH3 group of t-Bu(+) differs from the other two. In the Ar-tagged t-Bu(+) in vacuum, this group is predominantly polarized, showing three C-H stretch vibrations at 2913, 2965, and 3036 cm(-1) whereas the other two methyls are predominantly involved in strong hyperconjugation, yielding an intense triple IR band with a maximum at 2839 cm(-1). In a condensed phase, the bulk solvent effect promoted participation of the polarized CH3 group in additional hyperconjugation, decreasing its νCH3 frequencies by approximately 120 cm(-1), whereas frequencies of the other CH3 groups decreased by only ca. 4-10 cm(-1). This observation indicates that the influence of the condensed phase on t-Bu(+) stabilization is substantial. Thus, enhancement of H-bonding between t-Bu(+) and Anion(-) strengthens hyperconjugation and promotes further cation stabilization.

PMID:
26172244
DOI:
10.1021/acs.jpca.5b04657

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