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

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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Veröffentlicht in:Journal of organic chemistry 2019-09, Vol.84 (18), p.11724-11734
Hauptverfasser: Narayanan, Arjun, Kohno, Kazufumi, Nirmalchandar, Archith, Haiges, Ralf, Iakobson, George, Beier, Petr, Prakash, G. K. Surya
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container_end_page 11734
container_issue 18
container_start_page 11724
container_title Journal of organic chemistry
container_volume 84
creator Narayanan, Arjun
Kohno, Kazufumi
Nirmalchandar, Archith
Haiges, Ralf
Iakobson, George
Beier, Petr
Prakash, G. K. Surya
description 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.
doi_str_mv 10.1021/acs.joc.9b01622
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title Studies on Long-Lived (Pentafluorosulfanyl)phenyl-Substituted Carbocations
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