Do resonance-assisted intramolecular halogen bonds exist without a charge transfer and a sigma-hole?
Result description
To analyze the properties and mechanisms of six types of intramolecular resonance-assisted halogen bonds (Br center dot center dot center dot O, Cl center dot center dot center dot O, F center dot center dot center dot O, Br center dot center dot centerdot O, Cl center dot center dot center dot S and F center dot center dot center dot S), we have chosen the five-membered closed ring system X-C1R1=C3R2-C2R3=Y (X = Br, Cl & F; Y = O & S) of unsaturated compounds with the substituents NO2, CH3 and H. A total of 78 structures were investigated by quantum chemical calculations at the MP2/aug-cc-pVTZ level of theory. A molecular electrostatic potential (MESP) map reveals that the cusp point of the sigma-hole was not utilized but the belt point was used forall these intramolecular halogen-bonding interactions, indicating that all are electrostatic interactions. The halogen-bonding angle is below 100 degrees with the strongest interactions. The value of the nucleus-independent chemical shift
Keywords
The result's identifiers
Result code in IS VaVaI
Result on the web
DOI - Digital Object Identifier
Alternative languages
Result language
angličtina
Original language name
Do resonance-assisted intramolecular halogen bonds exist without a charge transfer and a sigma-hole?
Original language description
To analyze the properties and mechanisms of six types of intramolecular resonance-assisted halogen bonds (Br center dot center dot center dot O, Cl center dot center dot center dot O, F center dot center dot center dot O, Br center dot center dot centerdot O, Cl center dot center dot center dot S and F center dot center dot center dot S), we have chosen the five-membered closed ring system X-C1R1=C3R2-C2R3=Y (X = Br, Cl & F; Y = O & S) of unsaturated compounds with the substituents NO2, CH3 and H. A total of 78 structures were investigated by quantum chemical calculations at the MP2/aug-cc-pVTZ level of theory. A molecular electrostatic potential (MESP) map reveals that the cusp point of the sigma-hole was not utilized but the belt point was used forall these intramolecular halogen-bonding interactions, indicating that all are electrostatic interactions. The halogen-bonding angle is below 100 degrees with the strongest interactions. The value of the nucleus-independent chemical shift
Czech name
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Czech description
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Classification
Type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Result continuities
Project
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2015
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Physical Chemistry Chemical Physics
ISSN
1463-9076
e-ISSN
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Volume of the periodical
17
Issue of the periodical within the volume
41
Country of publishing house
GB - UNITED KINGDOM
Number of pages
13
Pages from-to
27496-27508
UT code for WoS article
000363193800028
EID of the result in the Scopus database
2-s2.0-84944339786
Basic information
Result type
Jx - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP
CF - Physical chemistry and theoretical chemistry
Year of implementation
2015