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

Natalia S. Soldatova, Pavel S. Postnikov, Vitalii V. Suslonov, Troyana Yu Kissler, Daniil M. Ivanov, Mekhman S. Yusubov, Bartomeu Galmés, Antonio Frontera, Vadim Yu Kukushkin

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

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 s-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.

Original languageEnglish
Pages (from-to)2230-2242
Number of pages13
JournalOrganic Chemistry Frontiers
Volume7
Issue number16
DOIs
Publication statusPublished - 21 Aug 2020

ASJC Scopus subject areas

  • Organic Chemistry

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