{"title":"Theoretical study of stability of dinitrosyl iron(i) complexes with thiocarbonyl ligands","authors":"V. B. Krapivin, V. B. Luzhkov, N. A. Sanina","doi":"10.1007/s11172-024-4435-z","DOIUrl":null,"url":null,"abstract":"<div><p>The binding energies of thioligands L of the general formula S=CR<sub>1</sub>R<sub>2</sub> in dinitrosyl iron complexes [Fe(NO)<sub>2</sub>L<sub>2</sub>]<sup>+</sup> (DNICs) were calculated using density functional theory methods. The TPSSH functional with the def2-TZVP basis set and the PCM–SMD polarizable continuum model were used. The reactions of abstraction of 14 thioamide and thiocarbonyl ligands and their replacement with a H<sub>2</sub>O molecule in the gas phase and aqueous medium were studied. It is found that the bond energies in the gas phase do not accurately characterize the stability of DNICs because of the high energy of reorganization of the reaction products upon their transition into the aqueous phase. Analysis of the structure—activity correlations revealed linear regression dependences of Fe—S bond energies on partial charges on S atoms and electronegativity of thioligands.</p></div>","PeriodicalId":756,"journal":{"name":"Russian Chemical Bulletin","volume":"73 11","pages":"3196 - 3203"},"PeriodicalIF":1.7000,"publicationDate":"2025-01-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Russian Chemical Bulletin","FirstCategoryId":"92","ListUrlMain":"https://link.springer.com/article/10.1007/s11172-024-4435-z","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The binding energies of thioligands L of the general formula S=CR1R2 in dinitrosyl iron complexes [Fe(NO)2L2]+ (DNICs) were calculated using density functional theory methods. The TPSSH functional with the def2-TZVP basis set and the PCM–SMD polarizable continuum model were used. The reactions of abstraction of 14 thioamide and thiocarbonyl ligands and their replacement with a H2O molecule in the gas phase and aqueous medium were studied. It is found that the bond energies in the gas phase do not accurately characterize the stability of DNICs because of the high energy of reorganization of the reaction products upon their transition into the aqueous phase. Analysis of the structure—activity correlations revealed linear regression dependences of Fe—S bond energies on partial charges on S atoms and electronegativity of thioligands.
期刊介绍：
Publishing nearly 500 original articles a year, by leading Scientists from Russia and throughout the world, Russian Chemical Bulletin is a prominent international journal. The coverage of the journal spans practically all areas of fundamental chemical research and is presented in five sections:
General and Inorganic Chemistry;
Physical Chemistry;
Organic Chemistry;
Organometallic Chemistry;
Chemistry of Natural Compounds and Bioorganic Chemistry.
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