铂配合物中σ-给体磷原子31P核磁共振位移的DFT计算

IF 1.1 3区化学 Q4 CHEMISTRY, INORGANIC & NUCLEAR

Russian Journal of Coordination Chemistry Pub Date : 2025-05-26 DOI:10.1134/S1070328424601389

S. A. Kondrashova, Sh. K. Latypov

{"title":"铂配合物中σ-给体磷原子31P核磁共振位移的DFT计算","authors":"S. A. Kondrashova, Sh. K. Latypov","doi":"10.1134/S1070328424601389","DOIUrl":null,"url":null,"abstract":"The scopes and limitations of available computational approaches for evaluating 31P NMR chemical shifts of σ-donor phosphorus atoms in platinum complexes were analyzed. It was shown that satisfactory accuracy can be achieved only when shielding is calculated within a fully relativistic formalism (mDKS). Geometry optimization at the PBE0/{6-31+G(d); Pt(SDD)} level was found to be optimal in terms of cost-to-accuracy ratio. The effectiveness of the proposed approach was demonstrated for the analysis of cis/trans isomerism in platinum complexes.","PeriodicalId":759,"journal":{"name":"Russian Journal of Coordination Chemistry","volume":"51 2","pages":"135 - 142"},"PeriodicalIF":1.1000,"publicationDate":"2025-05-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"DFT Calculations of 31P NMR Chemical Shifts of σ-Donor Phosphorus Atoms in Platinum Complexes\",\"authors\":\"S. A. Kondrashova, Sh. K. Latypov\",\"doi\":\"10.1134/S1070328424601389\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The scopes and limitations of available computational approaches for evaluating 31P NMR chemical shifts of σ-donor phosphorus atoms in platinum complexes were analyzed. It was shown that satisfactory accuracy can be achieved only when shielding is calculated within a fully relativistic formalism (mDKS). Geometry optimization at the PBE0/{6-31+G(d); Pt(SDD)} level was found to be optimal in terms of cost-to-accuracy ratio. The effectiveness of the proposed approach was demonstrated for the analysis of cis/trans isomerism in platinum complexes.\",\"PeriodicalId\":759,\"journal\":{\"name\":\"Russian Journal of Coordination Chemistry\",\"volume\":\"51 2\",\"pages\":\"135 - 142\"},\"PeriodicalIF\":1.1000,\"publicationDate\":\"2025-05-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Russian Journal of Coordination Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S1070328424601389\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Journal of Coordination Chemistry","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1134/S1070328424601389","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

摘要

分析了目前用于评价铂配合物中σ-给体磷原子31P核磁共振化学位移的计算方法的范围和局限性。结果表明，只有在完全相对论形式（mDKS）下计算屏蔽时，才能获得满意的精度。PBE0/{6-31+G(d)处的几何优化Pt(SDD)}水平在成本-准确率方面是最优的。该方法在铂配合物顺/反异构分析中的有效性得到了验证。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

查看原文本刊更多论文

DFT Calculations of 31P NMR Chemical Shifts of σ-Donor Phosphorus Atoms in Platinum Complexes

The scopes and limitations of available computational approaches for evaluating ³¹P NMR chemical shifts of σ-donor phosphorus atoms in platinum complexes were analyzed. It was shown that satisfactory accuracy can be achieved only when shielding is calculated within a fully relativistic formalism (mDKS). Geometry optimization at the PBE0/{6-31+G(d); Pt(SDD)} level was found to be optimal in terms of cost-to-accuracy ratio. The effectiveness of the proposed approach was demonstrated for the analysis of cis/trans isomerism in platinum complexes.

求助全文

通过发布文献求助，成功后即可免费获取论文全文。去求助

来源期刊

Russian Journal of Coordination Chemistry 化学-无机化学与核化学

CiteScore

2.40

自引率

15.80%

发文量

审稿时长

7.2 months

期刊介绍： Russian Journal of Coordination Chemistry is a journal that publishes reviews, original papers, and short communications on all aspects of theoretical and experimental coordination chemistry. Modern coordination chemistry is an interdisciplinary science that makes a bridge between inorganic, organic, physical, analytical, and biological chemistry.