Formation and Unimolecular Dehydrogenation of Gaseous Alkaline-earth Metal Amidoboranes M(NH2BH3)2 (M = Be - Ba): Comparative Computational Study
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- 作者：Anna S. Lisovenko and Alexey Y. Timoshkin
- 刊名：Zeitschrift für anorganische und allgemeine Chemie
- 出版年：2017
- 出版时间：January 2017
- 年：2017
- 卷：643
- 期：2
- 页码：209-213
- 全文大小：1099K
- ISSN：1521-3749
文摘
Formation of alkaline-earth metal amidoboranes M(NH2BH3)2 (M = Be, Mg, Ca, Sr, Ba) and unimolecular dehydrogenation reactions were computationally studied at the B3LYP/def2-TZVPPD level of theory. Formation of M(NH2BH3)2 from ammonia borane and MH2 is exergonic, but subsequent unimolecular dehydrogenation reactions are endergonic at room temperature. In contrast to alkali metal amidoboranes, for M(NH2BH3)2 the nature of M significantly affects their reactivity. Activation energies for the dehydrogenation of first and second hydrogen molecules decrease from Be to Ba. In case of Be compounds, intramolecular M···H–B contacts play an important role, whereas for heavier analogs such contacts are much less pronounced.