Heterolytic and homolytic C-D bond dissociation energies of NADH models in acetonitrile and primary isotopic effects on hydride versus hydrogen atom transfer reactions

作     者：CAO ChaoTun TAN Yue ZHU Xiao-Qing 

作者机构：State Key Laboratory of Elemento-Organic ChemistryDepartment of ChemistryNankai UniversityTianjin 300071China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2012年第55卷第10期

页      面：2054-2056页

核心收录：

学科分类：081704[工学-应用化学] 07[理学] 08[工学] 0817[工学-化学工程与技术] 070303[理学-有机化学] 0703[理学-化学] 

基　　金：support from the National Natural Science Foundation of China(21072104, 20921120403 and 20832004) the National Basic Research Program of China (2004CB719905) the 111 Project (B06005) is gratefully acknowledged 

主　　题：bond dissociation energies primary isotopic effects nicotinamide-adenine dinucleotide coenzyme models 

摘      要：Heterolytic and homolytic C D bond dissociation energies of three NADH models: BNAH-4,4-d 2 , HEH-4,4-d 2 and AcrD 2 in acetonitrile were first estimated by using an efficient method. The results showed that the heterolytic C D bond dissociation energies are 65.2, 70.2, and 81.9 kcal/mol and the homolytic C D bond dissociation energies are 72.66, 70.69, and 74.95 kcal/mol for BNAH-4,4-d 2 , HEH-4,4-d 2 , and AcrD 2 , respectively. According to the bond dissociation energy differences of isotope isomers, an interesting conclusion can be made that the primary kinetic isotope effects are dependent not only on the zero-point energy difference of the isotope isomers, but also on the types of C D bond dissociations, and the C D bond homolytic dissociations should have much larger primary kinetic isotope effects (26.9 28.8) than the corresponding C D bond heterolytic dissociations (3.9-5.4).