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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >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
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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

机译：2,7-二甲基-1,2,4-三氮杂锌的3,5-（Oxo /硫代）衍生物的反应性的计算研究。 keto-enol tautomerization和储氢潜力

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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 BH_(3) 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:BH_(3) complexes, accompanied by the loss of H_(2) molecular hydrogen, is a strongly exothermic process. With one triazepine the pathway for H_(2) elimination from [triazepine]-BH_(3) is characterized by a small energy barrier ranging from 11 to 23 kJ/mol. The second H_(2) 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)-BH_(2), 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 H_(2) storage applications.
机译：G4的理论水平用于评估一系列三氮杂胺的酸度，即3-硫代-5-氧代，5-硫代-3-氧代，3,5-二氧化硅和3,5-二氧基 - 衍生物为2,7-二甲基 - [1,2,4] - 三氮杂。还研究了可用的氮气孤牌液与BH_（3）形成的能力，以突出酸度的改变，并了解所形成的复合物的行为。还评估了氧气取代硫对复合物的稳定性和脱氢活化屏障的影响。这些三氮杂的形成：BH_（3）复合物，伴随着H_（2）分子氢的丧失，是强烈放热的过程。通过一种三氮杂卓，H_（2）的途径从[三氮杂] -BH_（3）的特征在于11至23kJ / mol的小能量屏障。第二H_（2）消除比第一个（〜27 kJ / mol）更高的能量。由于与添加两种三氮杂（三氮杂卓）_（2）-bH_（2）的添加相关的空间障碍，第三脱氢步骤比前述两个步骤相对较低，特别是在3,5的情况下 - 衍生物。探讨了与所有三唑衍生物的脱氢反应相关的潜在能量表面。本研究中报告的热力学利益可使三氮杂硼烷用作H_（2）储存应用的材料。

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