Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes

Yunzhou Chen; Huatian Shi; Chi Sing Lee; Shek-Man Yiu; Wai Lun Man; Tai-Chu Lau

doi:10.1021/jacs.1c07158

Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes

Yunzhou Chen, Huatian Shi, Chi Sing Lee, Shek-Man Yiu, Wai Lun Man^*, Tai-Chu Lau^*

^*Corresponding author for this work

Department of Chemistry

Research output: Contribution to journal › Journal article › peer-review

12 Citations (Scopus)

Abstract

Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, Co^III(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R′H) at ambient conditions (Co^III(qpy)OOR + R′H → Co^II(qpy) + R′^• + ROOH). The resulting alkyl radical (R′^•) reacts rapidly with O2 to form alkylperoxy radical (R′OO•), which is efficiently scavenged by Co^II(qpy) to give Co^III(qpy)OOR′ (Co^II(qpy) + R′OO^• → CoIII(qpy)OOR′). This unique reactivity enables Co^III(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R′H + O2 → R′OOH) under 1 atm air and at room temperature.

Original language	English
Pages (from-to)	14445–14450
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	143
Issue number	36
Early online date	3 Sept 2021
DOIs	https://doi.org/10.1021/jacs.1c07158
Publication status	Published - 15 Sept 2021

Scopus Subject Areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{ac58f18691e9492bb0148687070e6552,

title = "Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes",

abstract = "Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, CoIII(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R′H) at ambient conditions (CoIII(qpy)OOR + R′H → CoII(qpy) + R′• + ROOH). The resulting alkyl radical (R′•) reacts rapidly with O2 to form alkylperoxy radical (R′OO•), which is efficiently scavenged by CoII(qpy) to give CoIII(qpy)OOR′ (CoII(qpy) + R′OO• → CoIII(qpy)OOR′). This unique reactivity enables CoIII(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R′H + O2 → R′OOH) under 1 atm air and at room temperature.",

author = "Yunzhou Chen and Huatian Shi and Lee, {Chi Sing} and Shek-Man Yiu and Man, {Wai Lun} and Tai-Chu Lau",

note = "Funding Information: This work was financially supported by Interinstitutional Collaborative Research Scheme (RC-ICRS-18-19-01A) and Research Grants Council of Hong Kong (CityU 11301618, CityU 11302917, and HKBU 12300121). Y.C. acknowledges a Research Grant Studentship from Hong Kong Baptist University. W.-L.M. thanks Hong Kong Baptist University for the start-up grant. Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

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T1 - Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes

AU - Chen, Yunzhou

AU - Shi, Huatian

AU - Lee, Chi Sing

AU - Yiu, Shek-Man

AU - Man, Wai Lun

AU - Lau, Tai-Chu

N1 - Funding Information: This work was financially supported by Interinstitutional Collaborative Research Scheme (RC-ICRS-18-19-01A) and Research Grants Council of Hong Kong (CityU 11301618, CityU 11302917, and HKBU 12300121). Y.C. acknowledges a Research Grant Studentship from Hong Kong Baptist University. W.-L.M. thanks Hong Kong Baptist University for the start-up grant. Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/9/15

Y1 - 2021/9/15

N2 - Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, CoIII(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R′H) at ambient conditions (CoIII(qpy)OOR + R′H → CoII(qpy) + R′• + ROOH). The resulting alkyl radical (R′•) reacts rapidly with O2 to form alkylperoxy radical (R′OO•), which is efficiently scavenged by CoII(qpy) to give CoIII(qpy)OOR′ (CoII(qpy) + R′OO• → CoIII(qpy)OOR′). This unique reactivity enables CoIII(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R′H + O2 → R′OOH) under 1 atm air and at room temperature.

AB - Room temperature aerobic oxidation of hydrocarbons is highly desirable and remains a great challenge. Here we report a series of highly electrophilic cobalt(III) alkylperoxo complexes, CoIII(qpy)OOR supported by a planar tetradentate quaterpyridine ligand that can directly abstract H atoms from hydrocarbons (R′H) at ambient conditions (CoIII(qpy)OOR + R′H → CoII(qpy) + R′• + ROOH). The resulting alkyl radical (R′•) reacts rapidly with O2 to form alkylperoxy radical (R′OO•), which is efficiently scavenged by CoII(qpy) to give CoIII(qpy)OOR′ (CoII(qpy) + R′OO• → CoIII(qpy)OOR′). This unique reactivity enables CoIII(qpy)OOR to function as efficient catalysts for aerobic peroxidation of hydrocarbons (R′H + O2 → R′OOH) under 1 atm air and at room temperature.

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U2 - 10.1021/jacs.1c07158

DO - 10.1021/jacs.1c07158

M3 - Journal article

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JF - Journal of the American Chemical Society

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Room Temperature Aerobic Peroxidation of Organic Substrates Catalyzed by Cobalt(III) Alkylperoxo Complexes

Abstract

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