Theoretical study of protonation of the B10H10 2- anion and subsequent hydrogen removal due to substitution reaction in acidic mediumстатья

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[1] Kochnev V. K., Kuznetsov N. T. Theoretical study of protonation of the b10h10 2- anion and subsequent hydrogen removal due to substitution reaction in acidic medium // Computational and Theoretical Chemistry. — 2016. — Vol. 1075. — P. 77–81. The protonation of B10H10 2- in the presence of acetonitrile molecules has been studied using the Density Functional Theory on the B3LYP/6-31G* and more flexible B3LYP/6-311++G** levels. The B10H10 2- anion was surrounded by twenty acetonitrile molecules CH3CN to complete the first sphere of solvation, and H+ was added to the system. The protonation of B10H10 2- is regarded as a proton H* transfer from a nitrogen atom of protonated acetonitrile CH3CN·H+ to a facet of a boron cluster, accompanied by overcoming a small activation barrier of ca. 4.9 kcal/mol. The proton affinity (PA) of B10H10 2- in the presence of solvent molecules is ca. 8.7kcal/mol, which is much lower than that of the "bare" B10H10 2-. The effect of a solvent presence upon the isomerism of B10H11 - was studied, and it was shown that the local configuration of acetonitrile molecules facilitates the existence of BH2-isomers for B10H11 -. The removal of H2 from the formed B10H11 -·20CH3CN species was also investigated. In contrast to the "bare" B10H11 - that features different activation barriers for H2 removal from vertices with initial coordination number 6 or 5, the solvation facilitates this process only for the coordination number 6, while the other leads to the deprotonation of B10H11 - back to B10H10 2-. Estimated energy barrier value for hydrogen removal is ca. 23.6kcal/mol, which equals to boiling conditions in the case of actual experiment. One of the nearest CH3CN molecules substitutes instead of H2 giving B10H9(NCCH3)-. This reaction shows an exothermic effect of ca. 16.1 kcal/mol. © 2015 Elsevier B.V. [ DOI ]

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