Diaryliodonium as a double σ-hole donor: the dichotomy of thiocyanate halogen bonding provides divergent solid state arylation by diaryliodonium cations
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F20%3A43934080" target="_blank" >RIV/60461373:22310/20:43934080 - isvavai.cz</a>
Result on the web
<a href="http://DOI" target="_blank" >http://DOI</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1039/d0qo00678e" target="_blank" >10.1039/d0qo00678e</a>
Alternative languages
Result language
angličtina
Original language name
Diaryliodonium as a double σ-hole donor: the dichotomy of thiocyanate halogen bonding provides divergent solid state arylation by diaryliodonium cations
Original language description
X-ray crystallography data revealed the dichotomy of thiocyanate-involving noncovalent interactions in [(ArArI)-Ar-1-I-2](SCN), as reflected in the generation of two types of supramolecular aggregates: (i) previously unreported 4-membered heterotetramers (Ar-1/Ar-2= 4-ClC6H4/2,4,6-(MeO)(3)C6H2, 4-BrC6H4/2,4,6-(MeO)(3)C6H2; 2 examples) featuring exclusively halogen bond (XB)N-XB-bound SCN(-)anions, and (ii) the 8-membered cyclic heterotetramers (Ar-1/Ar-2= Ph/Ph, Ph/2,4,6-(MeO)(3)C6H2, 4-FC6H4/2,4,6-(MeO)(3)C6H2, 3,5-Me2C6H3/4-MeOC6H4, 3,5-Me2C6H3/2,4,6-(MeO)(3)C6H2; 5 examples) with twoN,S-XB-bound thiocyanates featuring both SMIDLINE HORIZONTAL ELLIPSISI and NMIDLINE HORIZONTAL ELLIPSISI noncovalent contacts. In all cases, the I(III)centers function as a double sigma-hole donor to provide two directional XBs. The XB preorganization affects the chemoselectivity of the thiocyanate arylation in the solid-state: the heating of [(ArArI)-Ar-1-I-2](SCN) exhibiting eitherN-, orN,Spreorganized XBs leads to extremely rareN-arylation or the conventionalS-arylation, respectively. The charge-assisted XBs in [(ArArI)-Ar-1-I-2](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 theN- andN,S-XB interactions was studied, including the recognition of energy differences between the IMIDLINE HORIZONTAL ELLIPSISN and IMIDLINE HORIZONTAL ELLIPSISS contacts. The computational data were useful to rationalize the divergent solid-stateN- orS-arylation of thiocyanates.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10401 - Organic chemistry
Result continuities
Project
—
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2020
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Organic Chemistry Frontiers
ISSN
2052-4129
e-ISSN
2052-4129
Volume of the periodical
7
Issue of the periodical within the volume
16
Country of publishing house
GB - UNITED KINGDOM
Number of pages
13
Pages from-to
2230-2242
UT code for WoS article
000558942300008
EID of the result in the Scopus database
2-s2.0-85091579523