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Tetravalent Oxygen and Sulphur Centres Mediated by Carborane Superacid: Theoretical Analysis |
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| Authors: | Prof. Sławomir J. Grabowski Prof. David Casanova Prof. Elena Formoso Prof. Jesus M. Ugalde |
| Affiliation: | 1. Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), P.K. 1072, 20080 Donostia, Euskadi, Spain;2. Donostia International Physics Center (DIPC), 20018 Donostia, Euskadi, Spain IKERBASQUE, Basque Foundation for Science, 48011 Bilbo, Euskadi, Spain;3. Donostia International Physics Center (DIPC), 20018 Donostia, Euskadi, Spain Farmazia Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), 01006 Vitoria-Gasteiz, Euskaldi, Spain;4. Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), P.K. 1072, 20080 Donostia, Euskadi, Spain Donostia International Physics Center (DIPC), 20018 Donostia, Euskadi, Spain |
| Abstract: | The tetravalent oxygen or sulphur centres, especially in H4O2+ and H4S2+ dications, were analysed experimentally and theoretically in various studies. Herein, we discuss stabilities of such centres in related H(CH3)3O2+ and H(CH3)3S2+ dications mediated by carborane superacid. The ωB97X-D/6-311++G(d,p) calculations were performed for a gas phase and for different solvents characterized by a wide range of dielectric constants for complexes of these dications with the conjugated base of H(CHB11F11) carborane superacid, CHB11F11−, which indicate that these complexes are linked by hydrogen bonds. The Quantum Theory of ‘Atoms in Molecules’ (QTAIM) approach is applied to characterize these interactions. DFT results show that tetravalent oxygen and sulphur structures are additionally stabilized by polar solvents. |
| Keywords: | carborane superacid density functional calculations hydrogen bond Quantum Theory of Atoms in Molecules tetravalent oxygen and sulphur |