Comparison of RC(=O)=OOH, RC(=O)O-OH and R(C=O)OO-H bond dissociation energies with RC-OOH, RCO-OH and RCOO-H, R as phenyl, vinyl and alkyl groups

Sebbar N; Bozzelli JW; Bockhorn H

Chemical Physics Letters, Vol.629, 102-112, 2015

DOI10.1016/j.cplett.2015.03.040 Export Citation

Comparison of RC(=O)=OOH, RC(=O)O-OH and R(C=O)OO-H bond dissociation energies with RC-OOH, RCO-OH and RCOO-H, R as phenyl, vinyl and alkyl groups

Sebbar N, Bozzelli JW, Bockhorn H

Bond dissociation energies (BDE) on a series of peracids RC(=O)OOH, hydroperoxides ROOH and the corresponding peroxy radicals RC(=O)OO center dot and RCOO center dot are calculated. BDE's are compared to provide information on influence of the carbonyl group (-C(=O)) on the bond dissociation energies in these systems. DFT, G3MP2B3 and G3 calculation methods with isodesmic reaction methods are used for the enthalpies. The RC(=O)=OOH, RC(=O)O-OH and RC(=O)OO-H bond energies are considerably stronger in systems containing the carbonyl group. The stronger BDE's to the carbonyl peroxy oxygen may provide increased stability for benzoyl and alkyl-carbonyl compared to alkyl peroxy nitrates. (C) 2015 Elsevier B.V. All rights reserved.