Diaryliodonium as a double ?-hole donor: the dichotomy of thiocyanate halogen bonding provides divergent solid state arylation by diaryliodonium cations

Detalhes bibliográficos
Parent link:	Organic Chemistry Frontiers Vol. 7, iss. 16.— 2020.— [P. 2230-2242]
Corporate Authors:	Национальный исследовательский Томский политехнический университет Исследовательская школа химических и биомедицинских технологий Научно-исследовательский центр "Онкотераностика", Национальный исследовательский Томский политехнический университет Исследовательская школа химических и биомедицинских технологий
Outros Autores:	Soldatova N. S. Nataljya Sergeevna, Postnikov P. S. Pavel Sergeevich, Suslonov V. V. Vitaly Valerjevich, Kissler T. Yu. Troyana, Ivanov D. M. Daniil Mikhaylovich, Yusubov M. S. Mekhman Suleiman-Ogly (Suleimanovich), Galmes B. Bartomeu, Frontera A. Antonio, Kukushkin V. Yu. Vadim
Resumo:	Title screen X-ray crystallography data revealed the dichotomy of thiocyanate-involving noncovalent interactions in [Ar1Ar2I](SCN), as reflected in the generation of two types of supramolecular aggregates: (i) previously unreported 4-membered heterotetramers (Ar1/Ar2 = 4-ClC6H4/2,4,6-(MeO)3C6H2, 4-BrC6H4/2,4,6-(MeO)3C6H2; 2 examples) featuring exclusively halogen bond (XB) N-XB-bound SCN− anions, and (ii) the 8-membered cyclic heterotetramers (Ar1/Ar2 = Ph/Ph, Ph/2,4,6-(MeO)3C6H2, 4-FC6H4/2,4,6-(MeO)3C6H2, 3,5-Me2C6H3/4-MeOC6H4, 3,5-Me2C6H3/2,4,6-(MeO)3C6H2; 5 examples) with two N,S-XB-bound thiocyanates featuring both S⋯I and N⋯I noncovalent contacts. In all cases, the IIII centers function as a double σ-hole donor to provide two directional XBs. The XB preorganization affects the chemoselectivity of the thiocyanate arylation in the solid-state: the heating of [Ar1Ar2I](SCN) exhibiting either N-, or N,S preorganized XBs leads to extremely rare N-arylation or the conventional S-arylation, respectively. The charge-assisted XBs in [Ar1Ar2I](SCN) were studied using density functional theory (DFT) calculations combined with a molecular electrostatic potential surface analysis and the quantum theory of atoms in molecules (QTAIM). Competition between the N- and N,S-XB interactions was studied, including the recognition of energy differences between the I⋯N and I⋯S contacts. The computational data were useful to rationalize the divergent solid-state N- or S-arylation of thiocyanates. Режим доступа: по договору с организацией-держателем ресурса
Idioma:	inglês
Publicado em:	2020
Assuntos:	электронный ресурс труды учёных ТПУ
Acesso em linha:	https://doi.org/10.1039/D0QO00678E
Formato:	Recurso Electrónico Capítulo de Livro
KOHA link:	https://koha.lib.tpu.ru/cgi-bin/koha/opac-detail.pl?biblionumber=663220