Icosahedral Carbaboranes with Peripheral Hydrogen–Chalcogenide Groups: Structures from Gas Electron Diffraction and Chemical Shielding in Solution

0500942 - ÚACH 2020 RIV DE eng J - Journal Article
Baše, Tomáš - Holub, Josef - Fanfrlík, Jindřich - Hnyk, Drahomír - Lane, P. D. - Wann, D. A. - Vishnevskiy, Y. V. - Tikhonov, D. S. - Reuter, C. G. - Mitzel, N. W.
Icosahedral Carbaboranes with Peripheral Hydrogen–Chalcogenide Groups: Structures from Gas Electron Diffraction and Chemical Shielding in Solution.
Chemistry - A European Journal. Roč. 25, č. 9 (2019), s. 2313-2321. ISSN 0947-6539. E-ISSN 1521-3765
R&D Projects: GA ČR(CZ) GA17-08045S
Institutional support: RVO:61388980 ; RVO:61388963
Keywords : ab initio calculations * carboranes * electron diffraction * selenols * thiols
OECD category: Inorganic and nuclear chemistry; Physical chemistry (UOCHB-X)
Impact factor: 4.857, year: 2019
Method of publishing: Limited access
https://onlinelibrary.wiley.com/doi/full/10.1002/chem.201805145

Carbaboranes 1,2-(EH)2-closo-1,2-C2B10H10 (E=S, Se) were prepared, in the case of E=Se for the first time. Their semi-experimental equilibrium molecular structures were established by the concerted use of quantum-chemical calculations and gas electron diffraction. A method was developed and implemented to quantify the contribution of experimental data to each refined structural parameter. The accuracy of the experimental structures and those calculated at the MP2 level of theory were gauged by comparison of experimental 11B NMR chemical shifts with quantum-chemically computed values, the inclusion of electron correlation (GIAO-MP2) provided superior results. For the purpose of geometrical prediction, the remaining group 16 elements were considered, and the icosahedral structures for E=O and Te were also computed, for E=O the same theoretical approach was used as for E=S, and for E=Te a description similar to that for E=Se was employed.
Permanent Link: http://hdl.handle.net/11104/0295231


Research data: Wiley onlinelibrary