Incorporation of Cation Affects the Redox Reactivity of Fe-NNN Complexes on C-H Oxidation
Issued Date
2022-07-25
Resource Type
ISSN
00201669
eISSN
1520510X
Scopus ID
2-s2.0-85135203235
Pubmed ID
35815773
Journal Title
Inorganic Chemistry
Volume
61
Issue
29
Start Page
11066
End Page
11074
Rights Holder(s)
SCOPUS
Bibliographic Citation
Inorganic Chemistry Vol.61 No.29 (2022) , 11066-11074
Suggested Citation
Teptarakulkarn P., Lorpaiboon W., Anusanti T., Laowiwatkasem N., Chainok K., Sangtrirutnugul P., Surawatanawong P., Chantarojsiri T. Incorporation of Cation Affects the Redox Reactivity of Fe-NNN Complexes on C-H Oxidation. Inorganic Chemistry Vol.61 No.29 (2022) , 11066-11074. 11074. doi:10.1021/acs.inorgchem.2c00762 Retrieved from: https://repository.li.mahidol.ac.th/handle/123456789/84179
Title
Incorporation of Cation Affects the Redox Reactivity of Fe-NNN Complexes on C-H Oxidation
Author's Affiliation
Other Contributor(s)
Abstract
Cations such as Lewis acids have been shown to enhance the catalytic activity of high-valent Fe-oxygen intermediates. Herein, we present a pyridine diamine ethylene glycol macrocycle, which can form Zn(II)-or Fe(III)-complex with the NNN site, while allowing redox-inactive cations to bind to the ethylene glycol moiety. The addition of alkali, alkali earth, and lanthanum ions resulted in positive shifts to the Fe(III/II) redox potential. Calculation of dissociation constants showed the tightest binding with a Ba2+ion. Density functional theory calculations were used to elucidate the effects of redox inactive cations toward the electronic structures of Fe complexes. Although the Fe-NNN complexes, both in the absence and presence of cations, can catalyze C-H oxidation of 9,10-dihydroanthracene, to give anthracene [hydrogen atom transfer (HAT) product], anthrone, and anthraquinone [oxygen atom transfer (OAT) products], highest overall activity and OAT/HAT product ratios were obtained in the presence of dications, that is, Ba2+and Mg2+, respectively.