Simple Route to [PSH][B9H14] and a Contemporary Study of Its Solid-State Dynamic Behavior

0575773 - ÚACH 2024 RIV US eng J - Článek v odborném periodiku
Bould, Jonathan - Londesborough, Michael Geoffrey Stephen - Brus, Jiří - Tok, Oleg L. - Sanz Miguel, P. J. - Macías, R.
Simple Route to [PSH][B9H14] and a Contemporary Study of Its Solid-State Dynamic Behavior.
Inorganic Chemistry. Roč. 62, č. 36 (2023), s. 14568-14579. ISSN 0020-1669. E-ISSN 1520-510X
Grant CEP: GA ČR(CZ) GA23-07563S
Institucionální podpora: RVO:61388980 ; RVO:61389013
Klíčová slova: Anions * Cations * Hydrogen * Ions * Salts
Obor OECD: Inorganic and nuclear chemistry; Polymer science (UMCH-V)
Impakt faktor: 4.6, rok: 2022
Způsob publikování: Omezený přístup
https://pubs.acs.org/doi/epdf/10.1021/acs.inorgchem.3c01665

The 1,8-bis(dimethylamino)naphthalenium ([PSH]+) decaborane salt, [PSH][B10H13], has been found to react in ethanol to form [PSH][B9H14] (1), affording a simple route to the synthesis of the arachno-nonaborate anion. This new polyhedral salt is characterized by NMR spectroscopy and X-ray diffraction. The measurement of diffusion coefficients by NMR methods demonstrates that the [PSH]+ cation and the [B9H14]- anion form ion pairs in a non-coordinating solvent such as CH2Cl2, whereas in CD3CN the formation of ion pairs was not observed. Insights into the long-known low-energy dynamic behavior, which involves the bridging and endo-terminal hydrogen atoms, are elucidated using DFT calculations. Salts [PSH][B9H14] (1) and [PSH][B9H14]·0.5CHCl3 (solvated, 1·0.5CHCl3) have also been studied by X-ray diffraction analysis. A solid-state NMR study has demonstrated that K[B9H14] and [PSH][B9H14] (1) undergo significantly different motion regimes, being a low-energy, weakly temperature-dependent process for 1, which may be ascribed to some type of low-amplitude reorientation of the whole boron cages. This process may be the mechanism for the low- to-room-temperature order-disorder hidden transition found by X-ray analysis.
Trvalý link: https://hdl.handle.net/11104/0345498


Vědecká data: CCDC