T. V. Krasnyakova, D. V. Nikitenko, S. A. Mitchenko
{"title":"PtII-NaI-С2Н3I-СН3I-Acetone 体系中的催化 C(sp2)-C(sp3)交电偶联","authors":"T. V. Krasnyakova, D. V. Nikitenko, S. A. Mitchenko","doi":"10.1134/S002315842401004X","DOIUrl":null,"url":null,"abstract":"<p>A new catalytic system for reductive С(<i>sp</i><sup>2</sup>)–C(<i>sp</i><sup>3</sup>) cross-electrophile coupling was designed: Pt<sup>II</sup> iodide complexes in an acetone solution of NaI catalyze the coupling of methyl iodide with vinyl iodide to form propylene. Simultaneously, a small amount of 1,3-butadiene, the product of C(<i>sp</i><sup>2</sup>)–C(<i>sp</i><sup>2</sup>) coupling, is released. The total yield of the products with respect to the reacted vinyl iodide is almost quantitative. In a large excess of CH<sub>3</sub>I, the C<sub>2</sub>H<sub>3</sub>I consumption is described by the pseudo-first-order kinetics. The cross-coupling occurs as the following sequence of steps: oxidative addition of CH<sub>3</sub>I to Pt<sup>II</sup> iodide complexes to form a methyl Pt<sup>IV</sup> complex → reduction of the methyl Pt<sup>IV</sup> complex with I<sup>–</sup> to form the corresponding Pt<sup>II</sup> derivative → oxidative addition of C<sub>2</sub>H<sub>3</sub>I to the Pt<sup>II</sup> derivative → reductive elimination of organyl ligands from the intermediate methyl vinyl Pt<sup>IV</sup> complex.</p>","PeriodicalId":682,"journal":{"name":"Kinetics and Catalysis","volume":"65 1","pages":"30 - 39"},"PeriodicalIF":1.3000,"publicationDate":"2024-04-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Catalytic C(sp2)–C(sp3) Cross-Electrophile Coupling in the PtII–NaI–С2Н3I–СН3I–Acetone System\",\"authors\":\"T. V. Krasnyakova, D. V. Nikitenko, S. A. Mitchenko\",\"doi\":\"10.1134/S002315842401004X\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>A new catalytic system for reductive С(<i>sp</i><sup>2</sup>)–C(<i>sp</i><sup>3</sup>) cross-electrophile coupling was designed: Pt<sup>II</sup> iodide complexes in an acetone solution of NaI catalyze the coupling of methyl iodide with vinyl iodide to form propylene. Simultaneously, a small amount of 1,3-butadiene, the product of C(<i>sp</i><sup>2</sup>)–C(<i>sp</i><sup>2</sup>) coupling, is released. The total yield of the products with respect to the reacted vinyl iodide is almost quantitative. In a large excess of CH<sub>3</sub>I, the C<sub>2</sub>H<sub>3</sub>I consumption is described by the pseudo-first-order kinetics. The cross-coupling occurs as the following sequence of steps: oxidative addition of CH<sub>3</sub>I to Pt<sup>II</sup> iodide complexes to form a methyl Pt<sup>IV</sup> complex → reduction of the methyl Pt<sup>IV</sup> complex with I<sup>–</sup> to form the corresponding Pt<sup>II</sup> derivative → oxidative addition of C<sub>2</sub>H<sub>3</sub>I to the Pt<sup>II</sup> derivative → reductive elimination of organyl ligands from the intermediate methyl vinyl Pt<sup>IV</sup> complex.</p>\",\"PeriodicalId\":682,\"journal\":{\"name\":\"Kinetics and Catalysis\",\"volume\":\"65 1\",\"pages\":\"30 - 39\"},\"PeriodicalIF\":1.3000,\"publicationDate\":\"2024-04-27\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Kinetics and Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://link.springer.com/article/10.1134/S002315842401004X\",\"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://link.springer.com/article/10.1134/S002315842401004X","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Catalytic C(sp2)–C(sp3) Cross-Electrophile Coupling in the PtII–NaI–С2Н3I–СН3I–Acetone System
A new catalytic system for reductive С(sp2)–C(sp3) cross-electrophile coupling was designed: PtII iodide complexes in an acetone solution of NaI catalyze the coupling of methyl iodide with vinyl iodide to form propylene. Simultaneously, a small amount of 1,3-butadiene, the product of C(sp2)–C(sp2) coupling, is released. The total yield of the products with respect to the reacted vinyl iodide is almost quantitative. In a large excess of CH3I, the C2H3I consumption is described by the pseudo-first-order kinetics. The cross-coupling occurs as the following sequence of steps: oxidative addition of CH3I to PtII iodide complexes to form a methyl PtIV complex → reduction of the methyl PtIV complex with I– to form the corresponding PtII derivative → oxidative addition of C2H3I to the PtII derivative → reductive elimination of organyl ligands from the intermediate methyl vinyl PtIV complex.
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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