A study of NMR parameters of para-substituted polyfluorinated benzyl cations and their precursors

A study of NMR parameters of para-substituted polyfluorinated benzyl cations and their precursors Full article

Journal

Journal of Fluorine Chemistry
ISSN: 0022-1139

Output data

Year: 2016, Volume: 182, Pages: 53-60 Pages count : 8 DOI: 10.1016/j.jfluchem.2015.12.003

Tags

NMR spectroscopy; DFT; SOPPA; Computation; Fluorinated; Benzyl carbocation

Authors

Fadeev Dmitriy S. ¹ , Chuikov Igor P. ¹ , Mamatyuk Victor I. ¹

Affiliations

1	(Данные Web of science) Russian Acad Sci, Siberian Branch, NN Vorozhtsov Novosibirsk Inst Organ Chem, Lavrentiev Ave 9, Novosibirsk 630090, Russia

C-13 and F-19 NMR spectra of a series of para-substituted heptafluorotoluenes and hexafluorobenzyl cations were analyzed. The quantum-chemical calculations of delta(13C) and delta(19F) chemical shifts (CSs) as well as F-19-F-19 and C-13-F-19 spin-spin coupling constants (SSCCs) were performed. F-19 and C-13 CSs were predicted by the GIAO/PBE/L22 method. The accuracy of theoretical CSs values increased in the computation for cations in conjunction with anions as ionic pairs. The computation by the SOPPA(CCSD) method had enough accuracy for the prediction of F-19-F-19,C-13-F-19 SSCCs and Ramsey contributions. Changes in various contributions to the spin-spin interaction along with their dependence on substituents at the para-position were also examined on passing from heptafluorotoluenes to the corresponding benzyl carbocations. (C) 2015 Elsevier B.V. All rights reserved.

Fadeev D.S. , Chuikov I.P. , Mamatyuk V.I.
A study of NMR parameters of para-substituted polyfluorinated benzyl cations and their precursors
Journal of Fluorine Chemistry. 2016. V.182. P.53-60. DOI: 10.1016/j.jfluchem.2015.12.003 WOS Scopus РИНЦ

Published print:

Feb 1, 2016

Web of science	WOS:000371188600009
Scopus	2-s2.0-84953286614
Elibrary	26929090
OpenAlex	W2266971718