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

Minaev, B. F., Minaeva, V. A., Panchenko, O. O., Bondarchuk, S. V. (2020) The low-lying triplet excited state of n-sulfinylanilines explains heir reactivity and inclination to cycloaddition across N–S=O ROUP. Voprosy khimii i khimicheskoi tekhnologii (№ 6). с. 106-114.

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Резюме

Density functional theory calculations for p-Br-N-sulfinylaniline and m-nitro-Nsulfinylaniline in the ground singlet (S0 ) and triplet (T1 ) excited states are presented and analyzed in terms of their specific physicochemical properties. As all aromatic Nsulfinylamines, 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 DielsAlder cycloaddition with dienes.

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