Effect of substituents in governing the homolytic gas-phase P–H bond dissociation enthalpies of phosphine-type oxides (R1R2P(=O)H)
OReilly R.J. Balanay M.P.
December 2024Elsevier B.V.
Chemical Data Collections
2024#54
This study reports the gas-phase homolytic P–H BDEs of a set of 30 phosphine-type oxides (i.e., R1R2P(=O)H) obtained using the W1w thermochemical protocol. We note that the P–H BDEs (at 298 K) of the species in this dataset differ by as much as 157.2 kJ mol–1, with (H2B)2P(=O)H having the lowest BDE (249.3 kJ mol–1) and F2P(=O)H having the highest (406.5 kJ mol–1). Furthermore, using the full set of 30 all-electron, non-relativistic, vibrationless bottom-of-the-well W1w P–H BDEs as reference values, we have identified several well-performing DFT methods that could be applied to the computation of the P–H BDEs of phosphine-type oxides. The best-performing DFTs (in conjunction with the AVTZ basis set) were shown to be MN12-SX (MAD = 1.7 kJ mol–1) and MN12-L (MAD = 2.7 kJ mol–1).
Bond dissociation energy , Homolytic dissociation , Phosphine oxide , Phosphorus-centered radicals , W1w theory
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Chemistry Department, School of Science and Technology, University of New England, Armidale, NSW, Australia
Department of Chemistry, School of Sciences and Humanities, Nazarbayev University, Astana, Kazakhstan
Chemistry Department
Department of Chemistry
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