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...

Full description

Saved in:
Bibliographic Details
Published in:Journal of organic chemistry 2019-09, Vol.84 (18), p.11724-11734
Main Authors: Narayanan, Arjun, Kohno, Kazufumi, Nirmalchandar, Archith, Haiges, Ralf, Iakobson, George, Beier, Petr, Prakash, G. K. Surya
Format: Article
Language:English
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.9b01622