取代基在调节膦类氧化物 (R1R2P(=O)H) 的均相气相 P-H 键解离焓方面的影响

IF 2.218 Q2 Chemistry Chemical Data Collections Pub Date : 2024-09-23 DOI:10.1016/j.cdc.2024.101164

Robert J. O'Reilly , Mannix P. Balanay

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引用次数: 0

摘要

本研究报告了利用 W1w 热化学协议获得的一组 30 种膦类氧化物（即 R1R2P(=O)H）的气相同解 P-H BDE。我们注意到，该数据集中各物种的 P-H BDE（298 K 时）相差高达 157.2 kJ mol-1，其中 (H2B)2P(=O)H 的 BDE 最低（249.3 kJ mol-1），F2P(=O)H 的 BDE 最高（406.5 kJ mol-1）。此外，利用全套 30 个全电子、非相对论、无振动井底 W1w P-H BDE 作为参考值，我们确定了几种性能良好的 DFT 方法，可用于计算膦类氧化物的 P-H BDE。结果表明，性能最好的 DFT 方法（结合 A'VTZ 基集）是 MN12-SX（MAD = 1.7 kJ mol-1）和 MN12-L（MAD = 2.7 kJ mol-1）。

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Effect of substituents in governing the homolytic gas-phase P–H bond dissociation enthalpies of phosphine-type oxides (R1R2P(=O)H)

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 A'VTZ basis set) were shown to be MN12-SX (MAD = 1.7 kJ mol^–1) and MN12-L (MAD = 2.7 kJ mol^–1).

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来源期刊

Chemical Data Collections Chemistry-Chemistry (all)

CiteScore

6.10

自引率

0.00%

发文量

169

审稿时长

24 days

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