Studies on Long-Lived (Pentafluorosulfanyl)phenyl-Substituted Carbocations

A variety of long-lived carbocations containing the p-(pentafluorosulfanyl)­phenyl and m-(pentafluorosulfanyl)­phenyl groups have been characterized by low-temperature NMR spectroscopy. In the case of potential nonclassical carbocations substituted with the p-(pentafluorosulfanyl)­phenyl substituent...

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Published inJournal of organic chemistry Vol. 84; no. 18; pp. 11724 - 11734
Main Authors Narayanan, Arjun, Kohno, Kazufumi, Nirmalchandar, Archith, Haiges, Ralf, Iakobson, George, Beier, Petr, Prakash, G. K. Surya
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 20.09.2019
Amer Chemical Soc
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
SOLVOLYTIC REACTIONS
NUCLEAR-MAGNETIC-RESONANCE
CARBONYL-COMPOUNDS
PERSULFONIUM SALTS
SUBSTITUENT CONSTANTS
GASSMAN-FENTIMAN TOOL
INCREASING-ELECTRON-DEMAND
GRIGNARD-REAGENTS
C-13 CHEMICAL-SHIFTS
STABLE CARBOCATIONS
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Summary:A variety of long-lived carbocations containing the p-(pentafluorosulfanyl)­phenyl and m-(pentafluorosulfanyl)­phenyl groups have been characterized by low-temperature NMR spectroscopy. In the case of potential nonclassical carbocations substituted with the p-(pentafluorosulfanyl)­phenyl substituent, deviations from linearity when the Hammett parameter (σC+ ) is plotted versus 13C NMR shifts of the carbocationic center were observed. Plotting the experimentally derived 13C NMR shifts versus σC+ or σ+ of classical 4-phenyl-X substituted carbocations also provides a means to accurately back-calculate the σ+ and σC+ parameters of the −SF5 substituent.
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ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b01622