Ten-vertex closo-carboranes react with “wet” fluoride: A direct closo-to-arachno transformation as a result of a hydride transfer

Holub, Josef; Bakardjiev, Mário; McKee, Michael L.; Hnyk, Drahomı́r

doi:10.1016/j.ica.2022.121000

Cited by 1 publication

(1 citation statement)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These reaction pathways have recently been searched computationally [12]; these attempts have shown that the products are negatively charged or neutral. The same applies to the reaction of this isomer with "wet" fluoride [13]. Such charge conditions are very common in boron cluster chemistry.…”

Section: Introductionmentioning

confidence: 83%

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

et al. 2023

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 83%