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Nitrosonium complexes of 2,11‐dithia‐5,6,8,9‐tetramethyl[3 2 ](1,4)cyclophane: a combined experimental and theoretical study
Author(s) -
Borodkin Gennady I.,
Elanov Innokenty R.,
Andreev Rodion V.,
Shakirov Makhmut M.,
Shubin Vyacheslav G.
Publication year - 2014
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3284
Subject(s) - chemistry , hexamethylbenzene , cyclophane , electrophile , crystallography , photochemistry , crystal structure , organic chemistry , catalysis , benzene
1 H and 13 C NMR studies and quantum chemical calculations show the interaction between 2,11‐dithia‐5,6,8,9‐tetramethyl[3 2 ](1,4)cyclophane and nitrosonium cation to result in the formation of π‐ and n ‐complexes. According to DFT/B3LYP/6‐31G(2d,p) calculations, formation of nitrosonium complexes is a strongly exothermic process both in gas phase and in SO 2 . Affinity of single‐charged complexes to NO + is usually larger than that of double‐charged and triple‐charged complexes, affinity of all the charged complexes to nitrosonium cation in SO 2 being larger than that in gas phase. The π‐complex with nitrosonium cation coordinated to the methylated aromatic ring is the most stable with structural characteristics being close to those obtained by X‐ray diffraction for nitrosonium π‐complexes of hexamethylbenzene and other arenes. The N―O bond lengths in all the complexes are quite close to each other and larger than that in NO + cation. The S―N bond length increases upon transition from single‐charged to double‐charged and polycharged complexes. Copyright © 2014 John Wiley & Sons, Ltd.