Dr. Vladimir Motornov, Martin Procházka, Nora Alpuente, Dr. Pedro Salvador, Prof. Petr Slavíček, Dr. Blanka Klepetářová, Prof. Xavi Ribas, Dr. Petr Beier
{"title":"引入弱配位三(三氟甲基)铜(III)","authors":"Dr. Vladimir Motornov, Martin Procházka, Nora Alpuente, Dr. Pedro Salvador, Prof. Petr Slavíček, Dr. Blanka Klepetářová, Prof. Xavi Ribas, Dr. Petr Beier","doi":"10.1002/ceur.202400004","DOIUrl":null,"url":null,"abstract":"<p>Tris(trifluoromethyl)copper(III), Cu(CF<sub>3</sub>)<sub>3</sub>, was prepared for the first time and fully characterized in the form of weakly coordinated highly reactive solvent neutral adducts (DMF)<sub>2</sub>Cu(CF<sub>3</sub>)<sub>3</sub> and (MeCN)Cu(CF<sub>3</sub>)<sub>3</sub>. Free Cu(CF<sub>3</sub>)<sub>3</sub> is an elusive molecule of distorted T-shaped geometry with Lewis acid properties, which is stabilized by solvation. Substitution of solvent molecules with monoanionic ligands in mild conditions afforded the first Cu(III)(CF<sub>3</sub>)<sub>3</sub> carboxylates [Cu(CF<sub>3</sub>)<sub>3</sub>(OAc)]<sup>−</sup> and [Cu(CF<sub>3</sub>)<sub>3</sub>(OBz)]<sup>−</sup> and Cu(III) nitrito complex [Cu(CF<sub>3</sub>)<sub>3</sub>(ONO)]<sup>−</sup>. An improved synthesis of valuable Grushin's trifluoromethylation reagents via the intermediacy of (MeCN)Cu(CF<sub>3</sub>)<sub>3</sub> was developed. (DMF)<sub>2</sub>Cu(CF<sub>3</sub>)<sub>3</sub> demonstrated promising properties in photoinduced radical C-H trifluoromethylation. Oxidation state theoretical studies showed the Cu(CF<sub>3</sub>)<sub>3</sub> compounds to be borderline between classical Cu(III) and inverted ligand field Cu(I) assignment.</p>","PeriodicalId":100234,"journal":{"name":"ChemistryEurope","volume":"2 2","pages":""},"PeriodicalIF":0.0000,"publicationDate":"2024-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400004","citationCount":"0","resultStr":"{\"title\":\"Introducing Weakly Ligated Tris(trifluoromethyl)copper(III)\",\"authors\":\"Dr. Vladimir Motornov, Martin Procházka, Nora Alpuente, Dr. Pedro Salvador, Prof. Petr Slavíček, Dr. Blanka Klepetářová, Prof. Xavi Ribas, Dr. Petr Beier\",\"doi\":\"10.1002/ceur.202400004\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Tris(trifluoromethyl)copper(III), Cu(CF<sub>3</sub>)<sub>3</sub>, was prepared for the first time and fully characterized in the form of weakly coordinated highly reactive solvent neutral adducts (DMF)<sub>2</sub>Cu(CF<sub>3</sub>)<sub>3</sub> and (MeCN)Cu(CF<sub>3</sub>)<sub>3</sub>. Free Cu(CF<sub>3</sub>)<sub>3</sub> is an elusive molecule of distorted T-shaped geometry with Lewis acid properties, which is stabilized by solvation. Substitution of solvent molecules with monoanionic ligands in mild conditions afforded the first Cu(III)(CF<sub>3</sub>)<sub>3</sub> carboxylates [Cu(CF<sub>3</sub>)<sub>3</sub>(OAc)]<sup>−</sup> and [Cu(CF<sub>3</sub>)<sub>3</sub>(OBz)]<sup>−</sup> and Cu(III) nitrito complex [Cu(CF<sub>3</sub>)<sub>3</sub>(ONO)]<sup>−</sup>. An improved synthesis of valuable Grushin's trifluoromethylation reagents via the intermediacy of (MeCN)Cu(CF<sub>3</sub>)<sub>3</sub> was developed. (DMF)<sub>2</sub>Cu(CF<sub>3</sub>)<sub>3</sub> demonstrated promising properties in photoinduced radical C-H trifluoromethylation. Oxidation state theoretical studies showed the Cu(CF<sub>3</sub>)<sub>3</sub> compounds to be borderline between classical Cu(III) and inverted ligand field Cu(I) assignment.</p>\",\"PeriodicalId\":100234,\"journal\":{\"name\":\"ChemistryEurope\",\"volume\":\"2 2\",\"pages\":\"\"},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2024-03-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ceur.202400004\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ChemistryEurope\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/ceur.202400004\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemistryEurope","FirstCategoryId":"1085","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/ceur.202400004","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
Tris(trifluoromethyl)copper(III), Cu(CF3)3, was prepared for the first time and fully characterized in the form of weakly coordinated highly reactive solvent neutral adducts (DMF)2Cu(CF3)3 and (MeCN)Cu(CF3)3. Free Cu(CF3)3 is an elusive molecule of distorted T-shaped geometry with Lewis acid properties, which is stabilized by solvation. Substitution of solvent molecules with monoanionic ligands in mild conditions afforded the first Cu(III)(CF3)3 carboxylates [Cu(CF3)3(OAc)]− and [Cu(CF3)3(OBz)]− and Cu(III) nitrito complex [Cu(CF3)3(ONO)]−. An improved synthesis of valuable Grushin's trifluoromethylation reagents via the intermediacy of (MeCN)Cu(CF3)3 was developed. (DMF)2Cu(CF3)3 demonstrated promising properties in photoinduced radical C-H trifluoromethylation. Oxidation state theoretical studies showed the Cu(CF3)3 compounds to be borderline between classical Cu(III) and inverted ligand field Cu(I) assignment.
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