TY - JOUR

T1 - Diaryliodonium as a double s-hole donor

T2 - The dichotomy of thiocyanate halogen bonding provides divergent solid state arylation by diaryliodonium cations

AU - Soldatova, Natalia S.

AU - Postnikov, Pavel S.

AU - Suslonov, Vitalii V.

AU - Kissler, Troyana Yu.

AU - Ivanov, Daniil M.

AU - Yusubov, Mekhman S.

AU - Galmés, Bartomeu

AU - Frontera, Antonio

AU - Kukushkin , Vadim Yu.

N1 - Publisher Copyright: © 2020 the Partner Organisations.

PY - 2020/8/21

Y1 - 2020/8/21

N2 - 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.

AB - 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.

KW - COMPLEXES

KW - FUNCTIONALIZATION

KW - HYPERVALENT IODINE REAGENTS

KW - IODONIUM SALTS

KW - MOLECULAR-CRYSTALS

KW - ONE-POT SYNTHESIS

KW - REACTIVITY

KW - SCN-CIRCLE-MINUS

KW - SOLVENT-FREE

KW - X-RAY-STRUCTURE

UR - http://www.scopus.com/inward/record.url?scp=85091579523&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/e82a31cc-62df-30c1-875f-61b5b0c66abf/

U2 - 10.1039/D0QO00678E

DO - 10.1039/D0QO00678E

M3 - Article

VL - 7

SP - 2230

EP - 2242

JO - Organic Chemistry Frontiers

JF - Organic Chemistry Frontiers

SN - 2052-4110

IS - 16

ER -