Boron-based octahedral dication experimentally detected: DFT surface confirms its availability

0573883 - ÚOCHB 2024 RIV GB eng J - Journal Article
Keller, W. - Sárosi, M. B. - Fanfrlík, Jindřich - Straka, Michal - Holub, Josef - McKee, M. L. - Hnyk, Drahomír
Boron-based octahedral dication experimentally detected: DFT surface confirms its availability.
RSC Advances. Roč. 13, č. 28 (2023), s. 19627-19637. E-ISSN 2046-2069
R&D Projects: GA ČR(CZ) GA22-03945S
Institutional support: RVO:61388963 ; RVO:61388980
Keywords : reaction pathway * dication * heteroborane cluster
OECD category: Physical chemistry; Inorganic and nuclear chemistry (UACH-T)
Impact factor: 3.9, year: 2022
Method of publishing: Open access
https://doi.org/10.1039/D3RA03665K

Borane and heteroborane clusters have been known as neutral or anionic species. In contrast to them, several ten-vertex monocationic nido and closo dicarbaborane-based systems have recently emerged from the reaction of the parent bicapped-square antiprismatic dicarbaboranes with N-heterocyclic carbenes followed by the protonization of the corresponding nido intermediates. The expansion of these efforts has afforded the very first closo-dicationic octahedral phosphahexaborane along with new closo-monocationic pnictogenahexaboranes of the same shapes. All are the products of the one-pot procedure that consists in the reaction of the same carbenes with the parent closo-1,2-Pn2B4Br4 (Pn = As, P). Whereas in the case of phosphorus such a monocation appears to be a mixture of stable intermediates, and arsenahexaboranyl monocation has occurred as the final product, all of them without using any subsequent reaction. The well-established DFT/ZORA/NMR approach has unambiguously confirmed the existence of these species in solution, and computed electrostatic potentials have revealed the delocalization of the positive charge in these monocations and in the very first dication, namely within the octahedral shapes in both cases.
Permanent Link: https://hdl.handle.net/11104/0344240