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

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

引用次数: 0

Abstract

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).

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

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

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）。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

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

期刊介绍： Chemical Data Collections (CDC) provides a publication outlet for the increasing need to make research material and data easy to share and re-use. Publication of research data with CDC will allow scientists to: -Make their data easy to find and access -Benefit from the fast publication process -Contribute to proper data citation and attribution -Publish their intermediate and null/negative results -Receive recognition for the work that does not fit traditional article format. The research data will be published as ''data articles'' that support fast and easy submission and quick peer-review processes. Data articles introduced by CDC are short self-contained publications about research materials and data. They must provide the scientific context of the described work and contain the following elements: a title, list of authors (plus affiliations), abstract, keywords, graphical abstract, metadata table, main text and at least three references. The journal welcomes submissions focusing on (but not limited to) the following categories of research output: spectral data, syntheses, crystallographic data, computational simulations, molecular dynamics and models, physicochemical data, etc.