A. O. Brovko, N. V. Kuratieva, V. A. Emelyanov, D. P. Pishchur, G. A. Kostin
{"title":"亚硝基钌与乙二胺和 NO-Ru-F 反式配位的新型异性配合物:合成、结构和光诱导连接异构化","authors":"A. O. Brovko, N. V. Kuratieva, V. A. Emelyanov, D. P. Pishchur, G. A. Kostin","doi":"10.1134/s0022476624070114","DOIUrl":null,"url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>A new method is proposed to synthesize ethylenediamine complex [RuNO(en)<sub>2</sub>OH]I<sub>2</sub> from K<sub>2</sub>[RuNOCl<sub>5</sub>], which increases the target product yield to 76%. Subsequent treatment of nitrate salt [RuNO(en)<sub>2</sub> OH](NO<sub>3</sub>)<sub>2</sub> with concentrated HF with the precipitation of HClO<sub>4</sub> gives [RuNO(en)<sub>2</sub>F](ClO<sub>4</sub>)<sub>2</sub> with a quantitative yield. According to the single crystal XRD data, in the [RuNO(en)<sub>2</sub>F]<sup>2+</sup> cationic moiety, nitrosyl and fluoride are in the <i>trans</i>-position relative to each other, and in the ruthenium coordination environment, the equatorial plane is composed of four nitrogen atoms from ethylenediamine ligands. The 450 nm light irradiation of the [RuNO(en)<sub>2</sub>F](ClO<sub>4</sub>)<sub>2</sub> complex at 80 K results in the formation of metastable linkage isomer MS1 with nitrosyl group coordination through the oxygen atom. According to the IR spectroscopic data, the population of MS1 is about 1%, and the respective vibrational band disappears when heated in a temperature range of 280-310 K. The activation parameters of the MS1–GS (ground state) transition according to the DSC data are <i>E</i><sub>a</sub> = 107.1±6.8 kJ/mol, ln<i>k</i><sub>0</sub> = 36.1±2.6.</p>","PeriodicalId":668,"journal":{"name":"Journal of Structural Chemistry","volume":null,"pages":null},"PeriodicalIF":1.2000,"publicationDate":"2024-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A New Heteroleptic Complex of Nitrosyl Ruthenium with Ethylenediamine and the NO–Ru–F Trans-Coordinate: Synthesis, Structure, and Photoinduced Linkage Isomerization\",\"authors\":\"A. O. Brovko, N. V. Kuratieva, V. A. Emelyanov, D. P. Pishchur, G. A. Kostin\",\"doi\":\"10.1134/s0022476624070114\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<h3 data-test=\\\"abstract-sub-heading\\\">Abstract</h3><p>A new method is proposed to synthesize ethylenediamine complex [RuNO(en)<sub>2</sub>OH]I<sub>2</sub> from K<sub>2</sub>[RuNOCl<sub>5</sub>], which increases the target product yield to 76%. Subsequent treatment of nitrate salt [RuNO(en)<sub>2</sub> OH](NO<sub>3</sub>)<sub>2</sub> with concentrated HF with the precipitation of HClO<sub>4</sub> gives [RuNO(en)<sub>2</sub>F](ClO<sub>4</sub>)<sub>2</sub> with a quantitative yield. According to the single crystal XRD data, in the [RuNO(en)<sub>2</sub>F]<sup>2+</sup> cationic moiety, nitrosyl and fluoride are in the <i>trans</i>-position relative to each other, and in the ruthenium coordination environment, the equatorial plane is composed of four nitrogen atoms from ethylenediamine ligands. The 450 nm light irradiation of the [RuNO(en)<sub>2</sub>F](ClO<sub>4</sub>)<sub>2</sub> complex at 80 K results in the formation of metastable linkage isomer MS1 with nitrosyl group coordination through the oxygen atom. According to the IR spectroscopic data, the population of MS1 is about 1%, and the respective vibrational band disappears when heated in a temperature range of 280-310 K. The activation parameters of the MS1–GS (ground state) transition according to the DSC data are <i>E</i><sub>a</sub> = 107.1±6.8 kJ/mol, ln<i>k</i><sub>0</sub> = 36.1±2.6.</p>\",\"PeriodicalId\":668,\"journal\":{\"name\":\"Journal of Structural Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.2000,\"publicationDate\":\"2024-07-26\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Structural Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1134/s0022476624070114\",\"RegionNum\":4,\"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":"Journal of Structural Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1134/s0022476624070114","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
A New Heteroleptic Complex of Nitrosyl Ruthenium with Ethylenediamine and the NO–Ru–F Trans-Coordinate: Synthesis, Structure, and Photoinduced Linkage Isomerization
Abstract
A new method is proposed to synthesize ethylenediamine complex [RuNO(en)2OH]I2 from K2[RuNOCl5], which increases the target product yield to 76%. Subsequent treatment of nitrate salt [RuNO(en)2 OH](NO3)2 with concentrated HF with the precipitation of HClO4 gives [RuNO(en)2F](ClO4)2 with a quantitative yield. According to the single crystal XRD data, in the [RuNO(en)2F]2+ cationic moiety, nitrosyl and fluoride are in the trans-position relative to each other, and in the ruthenium coordination environment, the equatorial plane is composed of four nitrogen atoms from ethylenediamine ligands. The 450 nm light irradiation of the [RuNO(en)2F](ClO4)2 complex at 80 K results in the formation of metastable linkage isomer MS1 with nitrosyl group coordination through the oxygen atom. According to the IR spectroscopic data, the population of MS1 is about 1%, and the respective vibrational band disappears when heated in a temperature range of 280-310 K. The activation parameters of the MS1–GS (ground state) transition according to the DSC data are Ea = 107.1±6.8 kJ/mol, lnk0 = 36.1±2.6.
期刊介绍:
Journal is an interdisciplinary publication covering all aspects of structural chemistry, including the theory of molecular structure and chemical bond; the use of physical methods to study the electronic and spatial structure of chemical species; structural features of liquids, solutions, surfaces, supramolecular systems, nano- and solid materials; and the crystal structure of solids.