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Computational Study on N–N Homolytic Bond Dissociation Enthalpies of Hydrazine Derivatives
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-02-22 00:00:00 , DOI: 10.1021/acs.jpca.7b12094 Yuanyuan Zheng 1 , Wenrui Zheng 1 , Jiaoyang Wang 1 , Huifang Chang 1 , Danfeng Zhu 1
The Journal of Physical Chemistry A ( IF 2.7 ) Pub Date : 2018-02-22 00:00:00 , DOI: 10.1021/acs.jpca.7b12094 Yuanyuan Zheng 1 , Wenrui Zheng 1 , Jiaoyang Wang 1 , Huifang Chang 1 , Danfeng Zhu 1
Affiliation
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The hydrazine derivatives have been regarded as the important building blocks in organic chemistry for the synthesis of organic N-containing compounds. It is important to understand the structure–activity relationship of the thermodynamics of N–N bonds, in particular, their strength as measured by using the homolytic bond dissociation enthalpies (BDEs). We calculated the N–N BDEs of 13 organonitrogen compounds by eight composite high-level ab initio methods including G3, G3B3, G4, G4MP2, CBS-QB3, ROCBS-QB3, CBS-Q, and CBS-APNO. Then 25 density functional theory (DFT) methods were selected for calculating the N–N BDEs of 58 organonitrogen compounds. The M05-2X method can provide the most accurate results with the smallest root-mean-square error (RMSE) of 8.9 kJ/mol. Subsequently, the N–N BDE predictions of different hydrazine derivatives including cycloalkylhydrazines, N-heterocyclic hydrazines, arylhydrazines, and hydrazides as well as the substituent effects were investigated in detail by using the M05-2X method. In addition, the analysis including the natural bond orbital (NBO) as well as the energies of frontier orbitals were performed in order to further understand the essence of the N–N BDE change patterns.
中文翻译：
肼衍生物N–N均质键解离焓的计算研究
肼衍生物被认为是有机化学中合成含氮有机化合物的重要组成部分。重要的是要了解N–N键的热力学的结构与活性之间的关系，特别是通过使用均聚物键解离焓（BDE）测得的强度。我们通过八个复合高级从头算出了13种有机氮化合物的N-BDEs。方法，包括G3，G3B3，G4，G4MP2，CBS-QB3，ROCBS-QB3，CBS-Q和CBS-APNO。然后选择25种密度泛函理论（DFT）方法来计算58种有机氮化合物的N–N BDE。M05-2X方法可以以8.9 kJ / mol的最小均方根误差（RMSE）提供最准确的结果。随后，使用M05-2X方法详细研究了不同肼衍生物（包括环烷基肼，N-杂环肼，芳基肼和酰肼）的N–BDE预测以及取代基的影响。此外，还进行了包括自然键轨道（NBO）以及前沿轨道能量的分析，以进一步了解N–BDE变化模式的本质。
更新日期：2018-02-22
中文翻译：
肼衍生物N–N均质键解离焓的计算研究
肼衍生物被认为是有机化学中合成含氮有机化合物的重要组成部分。重要的是要了解N–N键的热力学的结构与活性之间的关系，特别是通过使用均聚物键解离焓（BDE）测得的强度。我们通过八个复合高级从头算出了13种有机氮化合物的N-BDEs。方法，包括G3，G3B3，G4，G4MP2，CBS-QB3，ROCBS-QB3，CBS-Q和CBS-APNO。然后选择25种密度泛函理论（DFT）方法来计算58种有机氮化合物的N–N BDE。M05-2X方法可以以8.9 kJ / mol的最小均方根误差（RMSE）提供最准确的结果。随后，使用M05-2X方法详细研究了不同肼衍生物（包括环烷基肼，N-杂环肼，芳基肼和酰肼）的N–BDE预测以及取代基的影响。此外，还进行了包括自然键轨道（NBO）以及前沿轨道能量的分析，以进一步了解N–BDE变化模式的本质。
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