Homolytic C–O Cleavage in Phosphates and Sulfonates

The C–O homolytic bond dissociation enthalpies­(BDEs) were calculated by high-level ab initio including G4, G3B3, G3, CBS-QB3 and a series of density function theory (DFT) methods. It is found that the wB97 method gave the most reliable C–O BDEs and the root-mean-square deviation (RMSD) is 7.6 kJ/mo...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2015-04, Vol.119 (14), p.3488-3499
Main Authors: Ding, Lanlan, Zheng, Wenrui, Wang, Yingxing
Format: Article
Language:English
Subjects:
Carbon - chemistry
Molecular Structure
Oxygen - chemistry
Phosphates - chemistry
Quantum Theory
Sulfonic Acids - chemistry
Thermodynamics
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Summary:The C–O homolytic bond dissociation enthalpies­(BDEs) were calculated by high-level ab initio including G4, G3B3, G3, CBS-QB3 and a series of density function theory (DFT) methods. It is found that the wB97 method gave the most reliable C–O BDEs and the root-mean-square deviation (RMSD) is 7.6 kJ/mol. Therefore, the C­(sp2)-O BDE predictions and the substituent effects of alkenyl phosphates/sulfonates and aryl phosphates/sulfonates were investigated in detail by using the wB97 method. Interestingly, there exist different substituent effects in α- and β-substituted alkenyl phosphates/sulfonates. Excellent linear relationships between the C–O BDEs of β-substituted alkenyl phosphates/sulfonates with substituent constant σp + were found. In addition, the NBO analysis further disclosed the essence of the substituent effects on C–O BDEs.
ISSN:1089-5639
1520-5215
DOI:10.1021/acs.jpca.5b00569