Using phenyl cations as probes for establishing electrophilicity-nucleophilicity relations

The Journal of Organic Chemistry
Valentina DichiaranteAngelo Albini

Abstract

N,N-Dimethyl-4-aminophenyl cation is used as an electrophilic probe for determining the relative reactivity of nucleophiles. The singlet state (1 1) of this cation is completely unselective (reaction rates with benzene, MeCN, and trifluoroethanol within a factor of 5). The corresponding triplet (3 1) does not react with alcohols and MeCN. The rates of reaction of the latter intermediate with 23 pi, sigma, and n nucleophiles are measured by competition experiments and found to vary over only 2 orders of magnitude over a range of 22 units of the nucleophilicity parameter N introduced by Mayr. As far as one can judge with the considerable scatter of the data, fitting the data of both amines and pi nucleophiles is possible only by using a modified Mayr's equation: log k = s(E + eN) with e = 0.33. The reduced dependence on N is explained by the fact that in the case of diradicalic triplet 3 1 interaction with the nucleophile involves a half-filled (sigma) orbital, which is empty in singlet 11. It is suggested that Mayr's equation can be extended to quite diverse reactions, but a scaling factor of e < 1 may have to be introduced in some cases, according to the electronic structure of the electrophilic probe used.

References

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Citations

Jul 7, 2016·Organic & Biomolecular Chemistry·Michael Oelgemöller, Norbert Hoffmann
Jun 27, 2012·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Norbert Hoffmann
Nov 20, 2014·Faraday Discussions·Tomohiro ShirakiJeffrey S Moore
Sep 24, 2013·Photochemical & Photobiological Sciences : Official Journal of the European Photochemistry Association and the European Society for Photobiology·Dani SkalameraNikola Basarić
Apr 24, 2009·Organic Letters·Elisa FasaniAngelo Albini
Dec 22, 2009·The Journal of Organic Chemistry·Simone LazzaroniAngelo Albini
Mar 10, 2012·The Journal of Organic Chemistry·Erika AbitelliAngelo Albini
Apr 10, 2014·The Journal of Physical Chemistry. a·Sergey V Bondarchuk, Boris F Minaev
Nov 10, 2017·The Journal of Organic Chemistry·Đani ŠkalameraNikola Basarić

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