Determination of Standard Enthalpies of Formation of Organic Peroxides Using Calibration Dependencies

Abstract In the present work, the calibration dependencies for the M062X ( i =1),B3LYP ( i =2), wB97XD ( i =3), M08HX ( i =4), MN15 ( i =5), G3B3 ( i =6) and CBS‐QB3 ( i =7) and several other modeling approaches are determined using the calculated values of Δ ra H o of atomization and literature based values of Δ ra H o (X,TAB) of 14 reference peroxides. These calibration dependencies are used for the determination of Δ ra H o (X,CORR P ) i and Δ f H o (X,CORR P ) i of other peroxides. The coordination of values of Δ f H o (X,CORR P ) i ( i =1–7) by the intersection of their 3σ Pi intervals is used for the determination of the most consistent values of Δ f H o (X,MEAN P ). These values of Δ f H o (X,MEAN P ) are used for the determination of BDE of peroxides. It's demonstrated that the calculated and literature values of BDE are in agreement. Among the considered modeling approaches, the lowest uncertainties (σ Pi ) are determined for the G3B3 (3.1 kJ/mol), CBS‐QB3 (4.1 kJ/mol), and M062X/6‐311++G(d,p) (6.1 kJ/mol) approaches.