Articles producció científica> Química Física i Inorgànica

Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp(3))C-H Oxygenation of Oxazolidinones

  • Identification data

    Identifier: imarina:9295680
    Authors:
    Galushchinskiy AZou YOdutola JNikačević PShi JWTkachenko NLópez NFarràs PSavateev O
    Abstract:
    Graphitic carbon nitride (g-CN) is a transition metal free semiconductor that mediates a variety of photocatalytic reactions. Although photoinduced electron transfer is often postulated in the mechanism, proton-coupled electron transfer (PCET) is a more favorable pathway for substrates possessing X-H bonds. Upon excitation of an (sp(2))N-rich structure of g-CN with visible light, it behaves as a photobase-it undergoes reductive quenching accompanied by abstraction of a proton from a substrate. The results of modeling allowed us to identify active sites for PCET-the 'triangular pockets' on the edge facets of g-CN. We employ excited state PCET from the substrate to g-CN to selectively cleavethe endo-(sp(3))C-H bond in oxazolidine-2-ones followed by trapping the radical with O-2. This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of the apparent pK(a) value and modeling suggest that g-CN excited state can cleave X-H bonds that are characterized by bond dissociation free energy (BDFE) approximate to 100 kcal mol(-1).
  • Others:

    Author, as appears in the article.: Galushchinskiy A; Zou Y; Odutola J; Nikačević P; Shi JW; Tkachenko N; López N; Farràs P; Savateev O
    Department: Química Física i Inorgànica
    URV's Author/s: Lopez Alonso, Nuria / Nikacevic, Pavle
    Keywords: Transformation Poly(heptazine imides) Photooxidation Photocatalyst Photocatalysis Pcet Oxidation Oxazolidinone Light photoredox catalysis Lactams Dft Carbon nitride Amides
    Abstract: Graphitic carbon nitride (g-CN) is a transition metal free semiconductor that mediates a variety of photocatalytic reactions. Although photoinduced electron transfer is often postulated in the mechanism, proton-coupled electron transfer (PCET) is a more favorable pathway for substrates possessing X-H bonds. Upon excitation of an (sp(2))N-rich structure of g-CN with visible light, it behaves as a photobase-it undergoes reductive quenching accompanied by abstraction of a proton from a substrate. The results of modeling allowed us to identify active sites for PCET-the 'triangular pockets' on the edge facets of g-CN. We employ excited state PCET from the substrate to g-CN to selectively cleavethe endo-(sp(3))C-H bond in oxazolidine-2-ones followed by trapping the radical with O-2. This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of the apparent pK(a) value and modeling suggest that g-CN excited state can cleave X-H bonds that are characterized by bond dissociation free energy (BDFE) approximate to 100 kcal mol(-1).
    Thematic Areas: Química Medicina ii Medicina i Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias ii Ciências biológicas iii Ciências biológicas ii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Catalysis Astronomia / física
    licence for use: https://creativecommons.org/licenses/by/3.0/es/
    Author's mail: nuria.lopez@urv.cat pavle.nika@estudiants.urv.cat
    Record's date: 2024-08-03
    Papper version: info:eu-repo/semantics/publishedVersion
    Link to the original source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202301815
    Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
    Papper original source: Angewandte Chemie (International Ed. Print). 62 (18): e202301815-e202301815
    APA: Galushchinskiy A; Zou Y; Odutola J; Nikačević P; Shi JW; Tkachenko N; López N; Farràs P; Savateev O (2023). Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp(3))C-H Oxygenation of Oxazolidinones. Angewandte Chemie (International Ed. Print), 62(18), e202301815-e202301815. DOI: 10.1002/anie.202301815
    Article's DOI: 10.1002/anie.202301815
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2023
    Publication Type: Journal Publications
  • Keywords:

    Catalysis,Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary
    Transformation
    Poly(heptazine imides)
    Photooxidation
    Photocatalyst
    Photocatalysis
    Pcet
    Oxidation
    Oxazolidinone
    Light photoredox catalysis
    Lactams
    Dft
    Carbon nitride
    Amides
    Química
    Medicina ii
    Medicina i
    Materiais
    Interdisciplinar
    General medicine
    General chemistry
    Farmacia
    Engenharias ii
    Ciências biológicas iii
    Ciências biológicas ii
    Ciências biológicas i
    Chemistry, multidisciplinary
    Chemistry (miscellaneous)
    Chemistry (all)
    Chemistry
    Catalysis
    Astronomia / física
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