Author(s) |
O'Reilly, Robert J
Balanay, Mannix P
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Publication Date |
2024
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Abstract |
<p>This study reports the gas-phase homolytic P–H BDEs of a set of 30 phosphine-type oxides (<i>i.e.,</i> R<sup>1</sup>R<sup>2</sup>P(=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<sup>–1</sup>, with (H<sub>2</sub>B)<sub>2</sub>P(=O)H having the lowest BDE (249.3 kJ mol<sup>–1</sup>) and F<sub>2</sub>P(=O)H having the highest (406.5 kJ mol<sup>–1</sup>). 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 A'VTZ basis set) were shown to be MN12-SX (MAD = 1.7 kJ mol<sup>–1</sup>) and MN12-L (MAD = 2.7 kJ mol<sup>–1</sup>).</p>
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Citation |
Chemical Data Collections, v.54
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ISSN |
2405-8300
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Link | |
Publisher |
Elsevier BV
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Title |
Effect of substituents in governing the homolytic gas-phase P–H bond dissociation enthalpies of phosphine-type oxides (R1R2P(=O)H)
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Type of document |
Journal Article
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Entity Type |
Publication
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