دورية أكاديمية
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Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates.

التفاصيل البيبلوغرافية
العنوان: Electrophotocatalytic perfluoroalkylation by LMCT excitation of Ag(II) perfluoroalkyl carboxylates.
المؤلفون: Campbell BM; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States., Gordon JB; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States., Raguram ER; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States., Gonzalez MI; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States., Reynolds KG; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States., Nava M; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States.; Department of Chemistry and Biochemistry, University of California at Los Angeles, Los Angeles, CA 90095, United States., Nocera DG; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, MA 02138, United States.
المصدر: Science (New York, N.Y.) [Science] 2024 Jan 19; Vol. 383 (6680), pp. 279-284. Date of Electronic Publication: 2023 Dec 14.
نوع المنشور: Journal Article
اللغة: English
بيانات الدورية: Publisher: American Association for the Advancement of Science Country of Publication: United States NLM ID: 0404511 Publication Model: Print-Electronic Cited Medium: Internet ISSN: 1095-9203 (Electronic) Linking ISSN: 00368075 NLM ISO Abbreviation: Science Subsets: PubMed not MEDLINE; MEDLINE
أسماء مطبوعة: Publication: : Washington, DC : American Association for the Advancement of Science
Original Publication: New York, N.Y. : [s.n.] 1880-
مستخلص: Molecular Ag(II) complexes are superoxidizing photoredox catalysts capable of generating radicals from redox-reticent substrates. In this work, we exploited the electrophilicity of Ag(II) centers in [Ag(bpy) 2 (TFA)][OTf] and Ag(bpy)(TFA) 2 (bpy, 2,2'-bipyridine; OTf, CF 3 SO 3 - ) complexes to activate trifluoroacetate (TFA) by visible light-induced homolysis. The resulting trifluoromethyl radicals may react with a variety of arenes to forge C(sp 2 )-CF 3 bonds. This methodology is general and extends to other perfluoroalkyl carboxylates of higher chain length (R F CO 2 - ; R F , CF 2 CF 3 or CF 2 CF 2 CF 3 ). The photoredox reaction may be rendered electrophotocatalytic by regenerating the Ag(II) complexes electrochemically during irradiation. Electrophotocatalytic perfluoroalkylation of arenes at turnover numbers exceeding 20 was accomplished by photoexciting the Ag(II)-TFA ligand-to-metal charge transfer (LMCT) state, followed by electrochemical reoxidation of the Ag(I) photoproduct back to the Ag(II) photoreactant.
تواريخ الأحداث: Date Created: 20231214 Latest Revision: 20240118
رمز التحديث: 20240119
DOI: 10.1126/science.adk4919
PMID: 38096334
قاعدة البيانات: MEDLINE
الوصف
تدمد:1095-9203
DOI:10.1126/science.adk4919