Enthalpy of formation of 6-phenyl-1,5-diazabicyclo[3.1.0]hexane by combustion calorimetry and theoretical approach for efficient prediction of thermochemistry of diaziridines.

Autor: Lukyanova VA; Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russia. dorofeeva@phys.chem.msu.ru., Kuznetsov VV; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia., Konstantinova NM; Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russia. dorofeeva@phys.chem.msu.ru., Dmitrenok AS; N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, 119991 Moscow, Russia., Kosaya MP; Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russia. dorofeeva@phys.chem.msu.ru., Dorofeeva OV; Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russia. dorofeeva@phys.chem.msu.ru., Druzhinina AI; Department of Chemistry, M. V. Lomonosov Moscow State University, 119991 Moscow, Russia. dorofeeva@phys.chem.msu.ru.
Jazyk: angličtina
Zdroj: Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2023 Sep 27; Vol. 25 (37), pp. 25289-25298. Date of Electronic Publication: 2023 Sep 27.
DOI: 10.1039/d3cp03290f
Abstrakt: 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 1 )/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 ab initio 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.
Databáze: MEDLINE
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