Qian Xu, Li Deng, Er-Yong Liu, Lin-Mei Zhang, Shang-Fu Yuan*, Rui Zhou, Bingzhe Wang*, Dong-Sheng Li and Tao Wu*,
{"title":"硒化氢化铜簇用于可见光光催化炔烃的碘氟烷基化。","authors":"Qian Xu, Li Deng, Er-Yong Liu, Lin-Mei Zhang, Shang-Fu Yuan*, Rui Zhou, Bingzhe Wang*, Dong-Sheng Li and Tao Wu*, ","doi":"10.1021/acs.inorgchem.5c01517","DOIUrl":null,"url":null,"abstract":"<p >The photocatalytic iodofluoroalkylation of unsaturated systems is of great interest, with significant potential in the synthesis of fluorinated compounds. Herein, we introduce a selenate-protected <b>Cu</b><sub><b>18</b></sub> hydride cluster, [Cu<sub>18</sub>H<sub>9</sub>(dppy)<sub>6</sub>(PhCH<sub>2</sub>Se)<sub>6</sub>](PF<sub>6</sub>)<sub>3</sub> (dppy = diphenyl-2-pyridylphosphine, PhCH<sub>2</sub>Se = benzylselenate), that enables visible light-mediated iodofluoroalkylative difunctionalization of alkynes. Single crystal X-ray structural analysis reveals that the cluster comprises a hydride-embedded hexagonal close-packed Cu<sub>18</sub> kernel of the <i>D</i><sub>3<i>d</i></sub> symmetry, coprotected by benzylselenate and dppy ligands. Mechanistic studies suggest the reaction proceeds through a single-electron-transfer process from the photoexcited state [<b>Cu</b><sub><b>18</b></sub>are similar to those reported in The [<b>Cu</b><sub><b>18</b></sub>]<sup>+</sup> complexes then further oxidize the vinyl radicals to form vinyl cations, completing the redox-neutral catalytic cycle. This work presents an efficient method for synthesizing fluoroalkylated iodoalkenes and offers valuable insights into the design of catalytically active metal clusters for the advancement of organic synthesis.</p>","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"64 29","pages":"14902–14913"},"PeriodicalIF":4.7000,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Selenolated Copper Hydride Clusters for Visible-Light Photocatalytic Iodofluoroalkylation of Alkynes\",\"authors\":\"Qian Xu, Li Deng, Er-Yong Liu, Lin-Mei Zhang, Shang-Fu Yuan*, Rui Zhou, Bingzhe Wang*, Dong-Sheng Li and Tao Wu*, \",\"doi\":\"10.1021/acs.inorgchem.5c01517\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The photocatalytic iodofluoroalkylation of unsaturated systems is of great interest, with significant potential in the synthesis of fluorinated compounds. Herein, we introduce a selenate-protected <b>Cu</b><sub><b>18</b></sub> hydride cluster, [Cu<sub>18</sub>H<sub>9</sub>(dppy)<sub>6</sub>(PhCH<sub>2</sub>Se)<sub>6</sub>](PF<sub>6</sub>)<sub>3</sub> (dppy = diphenyl-2-pyridylphosphine, PhCH<sub>2</sub>Se = benzylselenate), that enables visible light-mediated iodofluoroalkylative difunctionalization of alkynes. Single crystal X-ray structural analysis reveals that the cluster comprises a hydride-embedded hexagonal close-packed Cu<sub>18</sub> kernel of the <i>D</i><sub>3<i>d</i></sub> symmetry, coprotected by benzylselenate and dppy ligands. Mechanistic studies suggest the reaction proceeds through a single-electron-transfer process from the photoexcited state [<b>Cu</b><sub><b>18</b></sub>are similar to those reported in The [<b>Cu</b><sub><b>18</b></sub>]<sup>+</sup> complexes then further oxidize the vinyl radicals to form vinyl cations, completing the redox-neutral catalytic cycle. This work presents an efficient method for synthesizing fluoroalkylated iodoalkenes and offers valuable insights into the design of catalytically active metal clusters for the advancement of organic synthesis.</p>\",\"PeriodicalId\":40,\"journal\":{\"name\":\"Inorganic Chemistry\",\"volume\":\"64 29\",\"pages\":\"14902–14913\"},\"PeriodicalIF\":4.7000,\"publicationDate\":\"2025-07-17\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Inorganic Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c01517\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.inorgchem.5c01517","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Selenolated Copper Hydride Clusters for Visible-Light Photocatalytic Iodofluoroalkylation of Alkynes
The photocatalytic iodofluoroalkylation of unsaturated systems is of great interest, with significant potential in the synthesis of fluorinated compounds. Herein, we introduce a selenate-protected Cu18 hydride cluster, [Cu18H9(dppy)6(PhCH2Se)6](PF6)3 (dppy = diphenyl-2-pyridylphosphine, PhCH2Se = benzylselenate), that enables visible light-mediated iodofluoroalkylative difunctionalization of alkynes. Single crystal X-ray structural analysis reveals that the cluster comprises a hydride-embedded hexagonal close-packed Cu18 kernel of the D3d symmetry, coprotected by benzylselenate and dppy ligands. Mechanistic studies suggest the reaction proceeds through a single-electron-transfer process from the photoexcited state [Cu18are similar to those reported in The [Cu18]+ complexes then further oxidize the vinyl radicals to form vinyl cations, completing the redox-neutral catalytic cycle. This work presents an efficient method for synthesizing fluoroalkylated iodoalkenes and offers valuable insights into the design of catalytically active metal clusters for the advancement of organic synthesis.
期刊介绍：
Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.
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