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

Robert J. O’Reilly, Amir Karton

2015

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DOI 10.1002/qua.25024
Data confidence 85 high
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Abstract

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