title: Accurate predictions of C-SO2R bond dissociation enthalpies using density functional theory methods.
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.
authors.affiliation: Department of Polymer Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China. dangzm@ustb.edu.cn.
authors.forename: Hai-Zhu
authors.initials: HZ
authors.lastname: Yu
authors.forename: Fang
authors.initials: F
authors.lastname: Fu
authors.forename: Liang
authors.initials: L
authors.lastname: Zhang
authors.forename: Yao
authors.initials: Y
authors.lastname: Fu
authors.forename: Zhi-Min
authors.initials: ZM
authors.lastname: Dang
authors.forename: Jing
authors.initials: J
authors.lastname: Shi
mesh_terms: D001665:Binding Sites; D002244:Carbon / Q000737:chemistry*; D003198:Computer Simulation; D004735:Energy Transfer; D008956:Models, Chemical; D008958:Models, Molecular; D013441:Sulfinic Acids / Q000737:chemistry*
chemical_list: D013441:Sulfinic Acids; D002244:Carbon