Reduction of Triple Bond in [B<sub>12</sub>H<sub>11</sub>NCR]<sup>−</sup> Anions by Lithium Aluminum Hydride: A Novel Approach to the Synthesis of N-Monoalkylammonio-Substituted <i>closo</i>-Dodecaborates
Alexey V. Nelyubin,
Nikolay K. Neumolotov,
Nikita A. Selivanov,
Alexander Yu. Bykov,
Ilya N. Klyukin,
Alexander S. Novikov,
Alexey S. Kubasov,
Andrey P. Zhdanov,
Konstantin Yu. Zhizhin,
Nikolay T. Kuznetsov
Affiliations
Alexey V. Nelyubin
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Nikolay K. Neumolotov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Nikita A. Selivanov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Alexander Yu. Bykov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Ilya N. Klyukin
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Alexander S. Novikov
Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7-9, 199034 Saint Petersburg, Russia
Alexey S. Kubasov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Andrey P. Zhdanov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Konstantin Yu. Zhizhin
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
Nikolay T. Kuznetsov
Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Leninskii Pr. 31, 119991 Moscow, Russia
By reacting nitrilium derivative of the closo-dodecaborate anion, Bu4N[B12H11N≡CR] (where R = Me, Et, nPr, iPr, p-tolyl), with lithium aluminum hydride (LiAlH4), N-alkylammonium derivatives of the closo-dodecaborate anion, and Bu4N[B12H11NH2CH2R], were obtained. The reduction reaction procedure was optimized, achieving yields close to quantitative (90–95%). The structure of the compound Bu4N[B12H11NH2CH2CH3] was determined using X-ray structural analysis. It was found that substituting lithium aluminum hydride (LiAlH4) with sodium borohydride (NaBH4) leads to the same products but only upon heating, while the reaction with LiAlH4 proceeds at room temperature.
