DFT Surface Infers Ten-Vertex Cationic Carboranes from the Corresponding Neutral closo Ten-Vertex Family: The Computed Background Confirming Their Experimental Availability

0571844 - ÚACH 2024 RIV CH eng J - Journal Article
McKee, M.L. - Vrána, J. - Holub, Josef - Fanfrlík, Jindřich - Hnyk, Drahomír
DFT Surface Infers Ten-Vertex Cationic Carboranes from the Corresponding Neutral closo Ten-Vertex Family: The Computed Background Confirming Their Experimental Availability.
Molecules. Roč. 28, č. 8 (2023), č. článku 3645. E-ISSN 1420-3049
R&D Projects: GA ČR(CZ) GA22-03945S
Institutional support: RVO:61388980 ; RVO:61388963
Keywords : carboranes * cations * DFT * N-heterocyclic carbenes * reaction pathways
OECD category: Inorganic and nuclear chemistry; Physical chemistry (UOCHB-X)
Impact factor: 4.6, year: 2022
Method of publishing: Open access

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.
Permanent Link: https://hdl.handle.net/11104/0342758