The low-lying triplet excited state of N-sulfinylanilines explains their reactivity and inclination to cycloaddition across N

The low-lying triplet excited state of N-sulfinylanilines explains their reactivity and inclination to cycloaddition across N–S=O group

Published:2020-12 Issue:6 Volume: Page:106-114
ISSN:0321-4095
Container-title:Voprosy Khimii i Khimicheskoi Tekhnologii
language:
Short-container-title:Vopr. Khim. Khim. Tekhnol.

Author:

Minaev B.F., ,Minaeva V.A.,Panchenko O.O.,Bondarchuk S.V., , ,

Abstract

Density functional theory calculations for p-Br-N-sulfinylaniline and m-nitro-N-sulfinylaniline in the ground singlet (S0) and triplet (T1) excited states are presented and analyzed in terms of their specific physicochemical properties. As all aromatic N-sulfinylamines, these compounds are rather unstable being sensitive to moist air and we assign this instability to the thermally allowed S0T1 excitation induced by internal magnetic forces. Our calculations indicate that the T1–S0 energy gap in these molecules is unexpectedly low and spin-orbit coupling matrix element between these states is relatively high, being allowed by the orbital symmetry selection rules. We also apply the exchange mechanism of spin-catalysis concept in order to explain the prone of N-sulfinylamines to the Diels-Alder cycloaddition with dienes.

Publisher

SHEI Ukrainian State University of Chemical Technology

Subject

Materials Chemistry,General Chemical Engineering,Environmental Chemistry,General Chemistry

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