Lukyanova Vera A, Kuznetsov Vladimir V, Konstantinova Natalia M, Dmitrenok Andrey S, Kosaya Maria P, Dorofeeva Olga V, Druzhinina Anna I
Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russia.
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia.
Phys Chem Chem Phys. 2023 Sep 27;25(37):25289-25298. doi: 10.1039/d3cp03290f.
The combustion energy and standard molar enthalpy of formation of crystalline 6-phenyl-1,5-diazabicyclo[3.1.0]hexane (PDABH) were determined using an isoperibolic calorimeter with a static bomb. PDABH is the first diaziridine for which the experimental value of the enthalpy of formation was obtained. This value was validated by the theoretical values of gas phase enthalpy of formation and enthalpy of sublimation. The gas phase enthalpy of formation was calculated using the DLPNO-CCSD(T)/CBS method in conjunction with isodesmic-type reactions. This method was chosen in comparison to another high quality evaluative method (G4), which has been shown to provide unreliable results for cyclic nitrogen containing compounds. The descriptors of the molecular electrostatic potential (MEP) were used to estimate the enthalpy of sublimation of PDABH. The proposed MEP model is based on experimental enthalpies of sublimation for 75 compounds structurally similar to PDABH. The high-level calculations of gas phase enthalpies of formation combined with enthalpies of sublimations estimated using descriptors of MEP allow predicting the enthalpies of formation of diaziridines in the solid phase.
使用带有静态弹的等压热量计测定了结晶态6-苯基-1,5-二氮杂双环[3.1.0]己烷（PDABH）的燃烧能量和标准摩尔生成焓。PDABH是首个获得生成焓实验值的二氮丙啶。该值通过气相生成焓和升华焓的理论值进行了验证。使用DLPNO-CCSD(T)/CBS方法结合等键型反应计算气相生成焓。与另一种高质量评估方法（G4）相比选择了该方法，已证明G4方法对含环氮化合物提供不可靠的结果。分子静电势（MEP）描述符用于估算PDABH的升华焓。所提出的MEP模型基于75种与PDABH结构相似的化合物的实验升华焓。气相生成焓的高水平计算与使用MEP描述符估算的升华焓相结合，能够预测固相中二氮丙啶的生成焓。
