Recent Advances and Advisable Applications of Bond Energetics in Organic Chemistry

Most organic transformation involves cleavage and formation of various covalent bonds, and naturally, can be regarded as a process of bond reorganization, which should be intrinsically related to bond energies (e.g., p K_a, BDE, etc.). However, in many cases such as in C-H bond activation/functionalization, direct correspondence between the bond energy and reaction rate or other relevant properties is only occasionally observed when applying the bond data by simple rules like the Linear Free-Energy Relationships (LFERs) in handling intricate reaction systems. In this Perspective, we present examples to argue that the above-mentioned situation is not a consequence of a diminishing role of the bond energetics in research, but most likely, comes from an improper use of energetic strategy, or simply due to a faulty selection of the data from unsuitable sources. Some advisable applications of bond energies in unscrambling the problems in modern day chemistry are exemplified through representative recent advances of the researches in this connection. Some of the possible directions of future research endeavors in the field of bond energetics and its prudent applications are recommended.