A dataset of highly accurate homolytic NBr bond dissociation energies obtained by Means of W2 theory

摘要: Homolytic NBr bond dissociation constitutes the initial step of numerous reactions involving N-brominated species. However, little is known about strength bonds toward homolytic cleavage. We herein report accurate energies (BDEs) for a set 18 molecules using high-level W2 thermochemical protocol. The BDEs (at 298 K) species in this range from 162.2 kJ mol−1 (N-bromopyrrole) to 260.6 ((CHO)2NBr). In order compute larger systems, which theory not applicable, we have benchmarked wide more economical theoretical procedures. Of these, G3-B3 offers best performance (root-mean-square deviations = 2.9 mol−1), and method, computed four widely used compounds. These include (BDEs are given parentheses): N-bromosuccinimide (281.6), N-bromoglutarimide (263.2), N-bromophthalimide (274.7), 1,3-dibromo-5,5-dimethylhydantoin (218.2 264.8 mol−1). © 2015 Wiley Periodicals, Inc.