Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranes

Golub, I.E.; Filippov, O.A.; Kulikova, V.A.; Belkova, N.V.; Epstein, L.M.; Shubina, E.S.

Авторы: Golub Igor E., Filippov Oleg A., Kulikova Vasilisa A., Belkova Natalia V., Epstein Lina M., Shubina Elena S.
Журнал: Molecules
Том: 25
Номер: 12
Год издания: 2020
Издательство: MDPI
Местоположение издательства: Basel, Switzerland
Номер статьи: 2920
DOI: 10.3390/molecules25122920
Аннотация: Thermodynamic hydricity (HDAMeCN) determined as Gibbs free energy (ΔG°[H]−) of the H− detachment reaction in acetonitrile (MeCN) was assessed for 144 small borane clusters (up to 5 boron atoms), polyhedral closo-boranes dianions [BnHn]2−, and their lithium salts Li2[BnHn] (n = 5–17) by DFT method [M06/6-311++G(d,p)] taking into account non-specific solvent effect (SMD model). Thermodynamic hydricity values of diborane B2H6 (HDAMeCN = 82.1 kcal/mol) and its dianion [B2H6]2− (HDAMeCN = 40.9 kcal/mol for Li2[B2H6]) can be selected as border points for the range of borane clusters’ reactivity. Borane clusters with HDAMeCN below 41 kcal/mol are strong hydride donors capable of reducing CO2 (HDAMeCN = 44 kcal/mol for HCO2−), whereas those with HDAMeCN over 82 kcal/mol, predominately neutral boranes, are weak hydride donors and less prone to hydride transfer than to proton transfer (e.g., B2H6, B4H10, B5H11, etc.). The HDAMeCN values of closo-boranes are found to directly depend on the coordination number of the boron atom from which hydride detachment and stabilization of quasi-borinium cation takes place. In general, the larger the coordination number (CN) of a boron atom, the lower the value of HDAMeCN.
Добавил в систему: Астахов Григорий Сергеевич

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Thermodynamic Hydricity of Small Borane Clusters and Polyhedral closo-Boranesстатья

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