A Broad View of Structure-Activity Relationship Performance for Alkanes and Haloalkanes
Résumé
As a subset of the gas kinetic database, the alkanes and haloalkanes possess some remarkable properties. Considering that they each share a common reaction mechanism with atmospheric oxidants, this group displays a wide range of reactivity. Furthermore, because of long-standing concerns over their effects upon climate, the ozone layer and climate, they have attracted a large amount of interest since the 1970s. As a result, there is a wealth of information that is known about them in terms of their kinetics, spectroscopy, thermodynamics and many other properties besides. The performances of the structure-activity relationships (SARs) and linear free-energy relationships (LFERs) that are available to the alkanes and haloalkanes are investigated. Well-known approaches such as the group-additivity approaches of Atkinson and co-workers and DeMore are found to perform well. However, there are many other methods including the LFERs between oxidants; with ionization potential; bond-dissociation energy; and other thermochemical approaches. These estimation methods also demonstrate good predictive power. Combining these developments with a new electrotopological approach that is unique to this study, a new level of coverage of the prediction-space of this family of compounds is achieved, and the possibility of an ensemble SAR prediction of rate coefficients is explored.
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