Accurate predictions of C-SO2R bond dissociation enthalpies using density functional theory methods.
Phys Chem Chem Phys
; 16(38): 20964-70, 2014 Oct 14.
Article
em En
| MEDLINE
| ID: mdl-25170742
ABSTRACT
The dissociation of the C-SO2R bond is frequently involved in organic and bio-organic reactions, and the C-SO2R bond dissociation enthalpies (BDEs) are potentially important for understanding the related mechanisms. The primary goal of the present study is to provide a reliable calculation method to predict the different C-SO2R bond dissociation enthalpies (BDEs). Comparing the accuracies of 13 different density functional theory (DFT) methods (such as B3LYP, TPSS, and M05 etc.), and different basis sets (such as 6-31G(d) and 6-311++G(2df,2p)), we found that M06-2X/6-31G(d) gives the best performance in reproducing the various C-S BDEs (and especially the C-SO2R BDEs). As an example for understanding the mechanisms with the aid of C-SO2R BDEs, some primary mechanistic studies were carried out on the chemoselective coupling (in the presence of a Cu-catalyst) or desulfinative coupling reactions (in the presence of a Pd-catalyst) between sulfinic acid salts and boryl/sulfinic acid salts.
Texto completo:
1
Base de dados:
MEDLINE
Assunto principal:
Ácidos Sulfínicos
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Carbono
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Modelos Moleculares
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Transferência de Energia
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Modelos Químicos
Tipo de estudo:
Prognostic_studies
/
Risk_factors_studies
Idioma:
En
Ano de publicação:
2014
Tipo de documento:
Article