Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp3)C−H Oxygenation of Oxazolidinones

Alexey Galushchinskiy; Yajun Zou; Jokotadeola Odutola; Pavle Nikačević; Jian Wen Shi; Nikolai Tkachenko; Núria López; Pau Farràs; Oleksandr Savateev

doi:10.1002/anie.202301815

Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp³)C−H Oxygenation of Oxazolidinones

Alexey Galushchinskiy
, Yajun Zou
, Jokotadeola Odutola
, Pavle Nikačević
, Jian Wen Shi
, Nikolai Tkachenko
, Núria López
, Pau Farràs
, Oleksandr Savateev^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

43 Citations (Scopus)

44 Downloads (Pure)

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 (sp²)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-(sp³)C−H bond in oxazolidine-2-ones followed by trapping the radical with O₂. 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) ≈100 kcal mol⁻¹.

Original language	English
Article number	e202301815
Journal	Angewandte Chemie - International Edition
Volume	62
Issue number	18
DOIs	https://doi.org/10.1002/anie.202301815
Publication status	Published - 2023
Publication type	A1 Journal article-refereed

Funding

This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska‐Curie grant agreement No. 861151 Solar2Chem. The material presented and views expressed here are the responsibility of the authors only. The EU Commission takes no responsibility for any use made of the information set out. Olaf Niemeyer (the head of NMR facility of the MPICI), Michael Born (electric workshop of the MPICI), Cliff Janiszewski (glass blowing workshop of the MPICI) and Jan von Szada‐Borryszkowski (mechanical workshop of the MPICI) are acknowledged for their contribution to this project. We thank BSC‐RES for providing generous computational time. Open Access funding enabled and organized by Projekt DEAL.

Keywords

Carbon Nitride
DFT
Oxazolidinone
PCET
Photocatalysis

Publication forum classification

Publication forum level 3

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202301815Licence: CC BY

Insights into the Role of GraphiticFinal published version, 6.38 MBLicence: CC BY

https://urn.fi/URN:NBN:fi:tuni-202304264482Licence: CC BY

Cite this

Galushchinskiy, A., Zou, Y., Odutola, J., Nikačević, P., Shi, J. W., 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 (sp³)C−H Oxygenation of Oxazolidinones. Angewandte Chemie - International Edition, 62(18), Article e202301815. https://doi.org/10.1002/anie.202301815

@article{bcf59f7aea4f4f0a9d2f319492510967,

title = "Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp3)C−H Oxygenation of Oxazolidinones",

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 (sp2)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 {\textquoteleft}triangular pockets{\textquoteright} on the edge facets of g-CN. We employ excited state PCET from the substrate to g-CN to selectively cleavethe endo-(sp3)C−H bond in oxazolidine-2-ones followed by trapping the radical with O2. This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of the apparent pKa value and modeling suggest that g-CN excited state can cleave X−H bonds that are characterized by bond dissociation free energy (BDFE) ≈100 kcal mol−1.",

keywords = "Carbon Nitride, DFT, Oxazolidinone, PCET, Photocatalysis",

author = "Alexey Galushchinskiy and Yajun Zou and Jokotadeola Odutola and Pavle Nika{\v c}evi{\'c} and Shi, \{Jian Wen\} and Nikolai Tkachenko and N{\'u}ria L{\'o}pez and Pau Farr{\`a}s and Oleksandr Savateev",

note = "Funding Information: This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Sk{\l}odowska‐Curie grant agreement No. 861151 Solar2Chem. The material presented and views expressed here are the responsibility of the authors only. The EU Commission takes no responsibility for any use made of the information set out. Olaf Niemeyer (the head of NMR facility of the MPICI), Michael Born (electric workshop of the MPICI), Cliff Janiszewski (glass blowing workshop of the MPICI) and Jan von Szada‐Borryszkowski (mechanical workshop of the MPICI) are acknowledged for their contribution to this project. We thank BSC‐RES for providing generous computational time. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: {\textcopyright} 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.",

year = "2023",

doi = "10.1002/anie.202301815",

language = "English",

volume = "62",

journal = "Angewandte Chemie - International Edition",

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publisher = "John Wiley \& Sons",

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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 (sp³)C−H Oxygenation of Oxazolidinones', Angewandte Chemie - International Edition, vol. 62, no. 18, e202301815. https://doi.org/10.1002/anie.202301815

Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp³)C−H Oxygenation of Oxazolidinones. / Galushchinskiy, Alexey; Zou, Yajun; Odutola, Jokotadeola et al.
In: Angewandte Chemie - International Edition, Vol. 62, No. 18, e202301815, 2023.

Research output: Contribution to journal › Article › Scientific › peer-review

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T1 - Insights into the Role of Graphitic Carbon Nitride as a Photobase in Proton-Coupled Electron Transfer in (sp3)C−H Oxygenation of Oxazolidinones

AU - Galushchinskiy, Alexey

AU - Zou, Yajun

AU - Odutola, Jokotadeola

AU - Nikačević, Pavle

AU - Shi, Jian Wen

AU - Tkachenko, Nikolai

AU - López, Núria

AU - Farràs, Pau

AU - Savateev, Oleksandr

N1 - Funding Information: This project has received funding from the European Union's Horizon 2020 research and innovation programme under the Marie Skłodowska‐Curie grant agreement No. 861151 Solar2Chem. The material presented and views expressed here are the responsibility of the authors only. The EU Commission takes no responsibility for any use made of the information set out. Olaf Niemeyer (the head of NMR facility of the MPICI), Michael Born (electric workshop of the MPICI), Cliff Janiszewski (glass blowing workshop of the MPICI) and Jan von Szada‐Borryszkowski (mechanical workshop of the MPICI) are acknowledged for their contribution to this project. We thank BSC‐RES for providing generous computational time. Open Access funding enabled and organized by Projekt DEAL. Publisher Copyright: © 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.

PY - 2023

Y1 - 2023

N2 - 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 (sp2)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-(sp3)C−H bond in oxazolidine-2-ones followed by trapping the radical with O2. This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of the apparent pKa value and modeling suggest that g-CN excited state can cleave X−H bonds that are characterized by bond dissociation free energy (BDFE) ≈100 kcal mol−1.

AB - 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 (sp2)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-(sp3)C−H bond in oxazolidine-2-ones followed by trapping the radical with O2. This reaction affords 1,3-oxazolidine-2,4-diones. Measurement of the apparent pKa value and modeling suggest that g-CN excited state can cleave X−H bonds that are characterized by bond dissociation free energy (BDFE) ≈100 kcal mol−1.

KW - Carbon Nitride

KW - DFT

KW - Oxazolidinone

KW - PCET

KW - Photocatalysis

U2 - 10.1002/anie.202301815

DO - 10.1002/anie.202301815

M3 - Article

AN - SCOPUS:85150897332

SN - 1433-7851

VL - 62

JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 18

M1 - e202301815

ER -