Computational study on alkenyl/aryl C(sp)-O homolytic cleavage of carboxylates and carbamates

The C-O homolytic bond dissociation enthalpies (BDEs) were evaluated by composite high-level G4 and 14 density function theory (DFT) methods. By comparing these DFT methods, the wB97 provided the most accurate results and the root mean square error (RMSE) is 7.6 kJ mol −1 for C-O BDE calculations. T...

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Bibliographic Details
Published in:RSC advances 2016-01, Vol.6 (32), p.26514-26525
Main Authors: Zheng, Wenrui, Ding, Lanlan, Wang, Jiaoyang, Wang, Yingxing
Format: Article
Language:English
Subjects:
Aromatic compounds
Bonding
Carboxylates
Chemical reactions
Cleavage
Density
Mathematical analysis
Nickel
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Summary:The C-O homolytic bond dissociation enthalpies (BDEs) were evaluated by composite high-level G4 and 14 density function theory (DFT) methods. By comparing these DFT methods, the wB97 provided the most accurate results and the root mean square error (RMSE) is 7.6 kJ mol −1 for C-O BDE calculations. Therefore, alkenyl and aryl C(sp 2 )-O cleavage and the substituent effect of carboxylates/carbamates were investigated by a wB97 method. Based on the mechanism of the Ni-catalyzed Suzuki-Miyaura cross-coupling reactions, the aryl C(sp 2 )-O BDEs and the substituent effect of Ni complexes of carboxylates/carbamates formed in the oxidative addition step were also discussed. In addition, the NBO analysis further disclosed the essence of the substituent effects on C-O BDEs. The alkenyl/aryl C(sp 2 )-O cleavage and the substituent effect in both carboxylates/carbamates and corresponding Ni complexes were investigated in detail by wB97 method.
ISSN:2046-2069
2046-2069
DOI:10.1039/c5ra27859g