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

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(T1)/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. High-level ab initio calculations of gas phase enthalpies of formation combined with enthalpies of sublimations estimated using descriptors of electrostatic potential allow predicting the enthalpies of formation of diaziridines in the solid phase.

Automated summary

This study determined the combustion energy and standard molar enthalpy of formation of PDABH using both experimental and theoretical methods. It also predicted the enthalpy of formation of PDABH in the solid phase.