A Systematic Evaluation of the N-F Bond Strength of Electrophilic N-F Reagents: Hints for Atomic Fluorine Donating Ability. 2017

Jin-Dong Yang, and Ya Wang, and Xiao-Song Xue, and Jin-Pei Cheng
State Key Laboratory of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, College of Chemistry, Nankai University , Tianjin 300071, China.

The recent discovery of the radical reactivity of a few traditionally electrophilic N-F reagents has sparked a renaissance of radical fluorination. A knowledge of the N-F bond dissociation enthalpies (BDE) of electrophilic N-F reagents is essential for understanding of their reactivities. However, a thorough literature survey revealed that such information is extremely sparse. This prompted us to carry out the first systematic computation on the N-F BDEs of electrophilic N-F reagents. The calculated N-F BDE scale of 88 electrophilic N-F reagents ranges from 49.3 to 80.0 kcal mol-1 in acetonitrile. The large variety of N-F reagents and wide span of N-F BDEs make the scale a useful tool not only for the future rational design of novel reagents but also for judicious selection of appropriate ones to explore new radical fluorinations.

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