T. V. Krasnyakova, D. V. Nikitenko, A. A. Gusev, V. G. But’ko, S. A. Mitchenko
{"title":"铂(II)碘配合物催化的碘化乙烯基同偶联反应：DFT 研究","authors":"T. V. Krasnyakova, D. V. Nikitenko, A. A. Gusev, V. G. But’ko, S. A. Mitchenko","doi":"10.1134/s0023158424601700","DOIUrl":null,"url":null,"abstract":"<h3 data-test=\"abstract-sub-heading\">Abstract</h3><p>The energy profile for vinyl iodide (RI) electrophile C(<i>sp</i><sup>2</sup>)–C(<i>sp</i><sup>2</sup>) homocoupling catalyzed by platinum(II) iodo complexes has been theoretically evaluated by the DFT method using the hybrid meta exchange-correlation functional M06 and the LANL2DZ basis set in the Gaussian09 software package. The reaction mechanism proposed earlier on the basis of experimental data was confirmed, consisting of the sequence of the following steps: R<sup>I</sup> oxidative addition to Pt<sup>II</sup> to form the intermediate compound RPt<sup>IV</sup>— reduction of the latter by iodide ions into RPt<sup>II</sup>—RI oxidative addition to form R<sub>2</sub>Pt<sup>IV</sup>—reductive elimination to yield the final butadiene-1,3. The highest activation barrier was found for the oxidative addition of the second vinyl iodide molecule, which is consistent with the experimental fact that the overall catalytic reaction rate is limited by just this step.</p>","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":null,"pages":null},"PeriodicalIF":1.3000,"publicationDate":"2024-09-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Vinyl Iodide Homocoupling Catalyzed by Platinum(II) Iodo Complexes: A DFT Study\",\"authors\":\"T. V. Krasnyakova, D. V. Nikitenko, A. A. Gusev, V. G. But’ko, S. A. Mitchenko\",\"doi\":\"10.1134/s0023158424601700\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<h3 data-test=\\\"abstract-sub-heading\\\">Abstract</h3><p>The energy profile for vinyl iodide (RI) electrophile C(<i>sp</i><sup>2</sup>)–C(<i>sp</i><sup>2</sup>) homocoupling catalyzed by platinum(II) iodo complexes has been theoretically evaluated by the DFT method using the hybrid meta exchange-correlation functional M06 and the LANL2DZ basis set in the Gaussian09 software package. The reaction mechanism proposed earlier on the basis of experimental data was confirmed, consisting of the sequence of the following steps: R<sup>I</sup> oxidative addition to Pt<sup>II</sup> to form the intermediate compound RPt<sup>IV</sup>— reduction of the latter by iodide ions into RPt<sup>II</sup>—RI oxidative addition to form R<sub>2</sub>Pt<sup>IV</sup>—reductive elimination to yield the final butadiene-1,3. The highest activation barrier was found for the oxidative addition of the second vinyl iodide molecule, which is consistent with the experimental fact that the overall catalytic reaction rate is limited by just this step.</p>\",\"PeriodicalId\":682,\"journal\":{\"name\":\"Kinetics and Catalysis\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.3000,\"publicationDate\":\"2024-09-04\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Kinetics and Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1134/s0023158424601700\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Kinetics and Catalysis","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1134/s0023158424601700","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Vinyl Iodide Homocoupling Catalyzed by Platinum(II) Iodo Complexes: A DFT Study
Abstract
The energy profile for vinyl iodide (RI) electrophile C(sp2)–C(sp2) homocoupling catalyzed by platinum(II) iodo complexes has been theoretically evaluated by the DFT method using the hybrid meta exchange-correlation functional M06 and the LANL2DZ basis set in the Gaussian09 software package. The reaction mechanism proposed earlier on the basis of experimental data was confirmed, consisting of the sequence of the following steps: RI oxidative addition to PtII to form the intermediate compound RPtIV— reduction of the latter by iodide ions into RPtII—RI oxidative addition to form R2PtIV—reductive elimination to yield the final butadiene-1,3. The highest activation barrier was found for the oxidative addition of the second vinyl iodide molecule, which is consistent with the experimental fact that the overall catalytic reaction rate is limited by just this step.
期刊介绍：
Kinetics and Catalysis Russian is a periodical that publishes theoretical and experimental works on homogeneous and heterogeneous kinetics and catalysis. Other topics include the mechanism and kinetics of noncatalytic processes in gaseous, liquid, and solid phases, quantum chemical calculations in kinetics and catalysis, methods of studying catalytic processes and catalysts, the chemistry of catalysts and adsorbent surfaces, the structure and physicochemical properties of catalysts, preparation and poisoning of catalysts, macrokinetics, and computer simulations in catalysis. The journal also publishes review articles on contemporary problems in kinetics and catalysis. The journal welcomes manuscripts from all countries in the English or Russian language.
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