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A Computational Study of the Reactivity of 3,5-(Oxo/Thioxo) Derivatives of 2,7-Dimethyl-1,2,4-Triazepines. Keto–Enol Tautomerization and Potential for Hydrogen Storage
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-02-27 00:00:00 , DOI: 10.1021/acs.jpca.8b00251 M’hamed Esseffar 1 , Carol A. Parish 2 , R. Jalal 3 , Al Mokhtar Lamsabhi
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-02-27 00:00:00 , DOI: 10.1021/acs.jpca.8b00251 M’hamed Esseffar 1 , Carol A. Parish 2 , R. Jalal 3 , Al Mokhtar Lamsabhi
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The G4 level of theory was used to evaluate the acidity of a series of triazepines, that is, 3-thioxo-5-oxo-, 5-thioxo-3-oxo-, 3,5-dioxo-, and 3,5-dithioxo- derivatives of 2,7-dimethyl-[1,2,4]-triazepine. The ability of their available nitrogen lone pair to form a dative bond with BH3 was also studied to highlight the resulting changes in acidity and to understand the behavior of the complexes formed. The effect of the substitution of sulfur by oxygen on the stability of the complex and the activation barrier of dehydrogenation was also evaluated. The formation of these triazepine:BH3 complexes, accompanied by the loss of H2 molecular hydrogen, is a strongly exothermic process. With one triazepine the pathway for H2 elimination from [triazepine]-BH3 is characterized by a small energy barrier ranging from 11 to 23 kJ/mol. The second H2 elimination is relatively more energetic than the first one (∼27 kJ/mol). Because of the steric hindrance associated with the addition of two molecules of triazepine (triazepine)2-BH2, the third dehydrogenation step is relatively less favorable than the two preceding steps, particularly in the case of the 3,5-dithio- derivative. The potential energy surface associated with the dehydrogenation reaction of all triazepine derivatives was explored. The thermodynamic favorability reported in this study could allow triazepine-borane to be used as a material for H2 storage applications.
中文翻译：
2,7-二甲基-1,2,4-三氮杂卓的3,5-（Oxo / Thioxo）衍生物反应性的计算研究。酮-烯醇互变异构化和储氢潜力
G4理论水平用于评估一系列三氮杂卓的酸度，即3-thioxo-5-oxo-，5-thioxo-3-oxo-，3,5-dioxo-和3,5- 2,7-二甲基-[1,2,4]-三氮杂卓的二硫代-衍生物。还研究了其可用的氮孤对与BH 3形成键的能力，以突出酸度的最终变化并了解所形成的配合物的行为。还评估了用氧气取代硫对配合物稳定性和脱氢活化势垒的影响。这些triazepine：BH 3配合物的形成，伴随着H 2分子氢的损失，是一个强烈的放热过程。使用一个三氮平时，H 2的途径从[三氮杂] -BH 3中消除的特征在于小的能量势垒，范围为11至23 kJ / mol。第二种H 2的消除相对比第一种具有更高的能量（〜27 kJ / mol）。由于与添加两个分子的三氮平（triazepine ）2 -BH 2有关的位阻，因此第三脱氢步骤相对于前两个步骤相对较不利，特别是在3,5-二硫代衍生物的情况下。探索了与所有三氮杂苯衍生物的脱氢反应相关的势能表面。这项研究中报道的热力学倾向性可以使三氮杂硼烷用作H 2储存应用的材料。
更新日期：2018-02-27
中文翻译：
2,7-二甲基-1,2,4-三氮杂卓的3,5-（Oxo / Thioxo）衍生物反应性的计算研究。酮-烯醇互变异构化和储氢潜力
G4理论水平用于评估一系列三氮杂卓的酸度，即3-thioxo-5-oxo-，5-thioxo-3-oxo-，3,5-dioxo-和3,5- 2,7-二甲基-[1,2,4]-三氮杂卓的二硫代-衍生物。还研究了其可用的氮孤对与BH 3形成键的能力，以突出酸度的最终变化并了解所形成的配合物的行为。还评估了用氧气取代硫对配合物稳定性和脱氢活化势垒的影响。这些triazepine：BH 3配合物的形成，伴随着H 2分子氢的损失，是一个强烈的放热过程。使用一个三氮平时，H 2的途径从[三氮杂] -BH 3中消除的特征在于小的能量势垒，范围为11至23 kJ / mol。第二种H 2的消除相对比第一种具有更高的能量（〜27 kJ / mol）。由于与添加两个分子的三氮平（triazepine ）2 -BH 2有关的位阻，因此第三脱氢步骤相对于前两个步骤相对较不利，特别是在3,5-二硫代衍生物的情况下。探索了与所有三氮杂苯衍生物的脱氢反应相关的势能表面。这项研究中报道的热力学倾向性可以使三氮杂硼烷用作H 2储存应用的材料。
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