DFT Surface Infers Ten-Vertex Cationic Carboranes from the Corresponding Neutral closo Ten-Vertex Family: The Computed Background Confirming Their Experimental Availability
Result description
Modern computational protocols based on the density functional theory (DFT) infer that polyhedral closo ten-vertex carboranes are key starting stationary states in obtaining ten-vertex cationic carboranes. The rearrangement of the bicapped square polyhedra into decaborane-like shapes with open hexagons in boat conformations is caused by attacks of N-heterocyclic carbenes (NHCs) on the closo motifs. Single-point computations on the stationary points found during computational examinations of the reaction pathways have clearly shown that taking the “experimental” NHCs into account requires the use of dispersion correction. Further examination has revealed that for the purposes of the description of reaction pathways in their entirety, i.e., together with all transition states and intermediates, a simplified model of NHCs is sufficient. Many of such transition states resemble in their shapes those that dictate Z-rearrangement among various isomers of closo ten-vertex carboranes. Computational results are in very good agreement with the experimental findings obtained earlier.
Keywords
carboranescationsDFTN-heterocyclic carbenesreaction pathways
The result's identifiers
Result code in IS VaVaI
Alternative codes found
RIV/61388963:_____/23:00571844 RIV/00216275:25310/23:39921146
Result on the web
DOI - Digital Object Identifier
Alternative languages
Result language
angličtina
Original language name
DFT Surface Infers Ten-Vertex Cationic Carboranes from the Corresponding Neutral closo Ten-Vertex Family: The Computed Background Confirming Their Experimental Availability
Original language description
Modern computational protocols based on the density functional theory (DFT) infer that polyhedral closo ten-vertex carboranes are key starting stationary states in obtaining ten-vertex cationic carboranes. The rearrangement of the bicapped square polyhedra into decaborane-like shapes with open hexagons in boat conformations is caused by attacks of N-heterocyclic carbenes (NHCs) on the closo motifs. Single-point computations on the stationary points found during computational examinations of the reaction pathways have clearly shown that taking the “experimental” NHCs into account requires the use of dispersion correction. Further examination has revealed that for the purposes of the description of reaction pathways in their entirety, i.e., together with all transition states and intermediates, a simplified model of NHCs is sufficient. Many of such transition states resemble in their shapes those that dictate Z-rearrangement among various isomers of closo ten-vertex carboranes. Computational results are in very good agreement with the experimental findings obtained earlier.
Czech name
—
Czech description
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Classification
Type
Jimp - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
—
OECD FORD branch
10402 - Inorganic and nuclear chemistry
Result continuities
Project
GA22-03945S: Polyhedral (Car)boranes; Cationic and Catalytically Applicable
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Molecules
ISSN
1420-3049
e-ISSN
1420-3049
Volume of the periodical
28
Issue of the periodical within the volume
8
Country of publishing house
CH - SWITZERLAND
Number of pages
13
Pages from-to
3645
UT code for WoS article
000982918200001
EID of the result in the Scopus database
2-s2.0-85156094403
Result type
Jimp - Article in a specialist periodical, which is included in the Web of Science database
OECD FORD
Inorganic and nuclear chemistry
Year of implementation
2023