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A Highly Reactive Chromium(V)-Oxo TAML Cation Radical Complex in Electron Transfer and Oxygen Atom Transfer Reactions

Title
A Highly Reactive Chromium(V)-Oxo TAML Cation Radical Complex in Electron Transfer and Oxygen Atom Transfer Reactions
Authors
Hong, Young HyunJang, YuriEzhov, RomanSeo, Mi SookLee, Yong-MinPandey, BhawanaHong, SeungwooPushkar, YuliaFukuzumi, ShunichiNam, Wonwoo
Ewha Authors
남원우Shunichi Fukuzumi서미숙
SCOPUS Author ID
남원우scopus; Shunichi Fukuzumiscopus; 서미숙scopus
Issue Date
2021
Journal Title
ACS CATALYSIS
ISSN
2155-5435JCR Link
Citation
ACS CATALYSIS vol. 11, no. 5, pp. 2889 - 2901
Keywords
electron transferoxygen atom transferchromium(V)-oxo complexredox-inactive metal ionreorganization energy
Publisher
AMER CHEMICAL SOC
Indexed
SCIE; SCOPUS WOS
Document Type
Article
Abstract
We report the synthesis, characterization, and electron-transfer (ET) oxidation reactivity of a chromium(V)-oxo TAML cation radical complex binding Sc3+ ion, {[ Cr-V(O)(TAML(center dot+))]-Sc3+}(3+) (2-Sc). Its precursors, such as [Cr-V(O)(TAML)](-) (1) and {[Cr-V(O)(TAML)]Sc3+}(2+) (1-Sc), were also characterized spectroscopically and/or structurally. In ET and oxygen atom transfer (OAT) reactions, while 1 and 1-Sc were sluggish oxidants, 2-Sc was a highly reactive oxidant with an extremely small reorganization energy. For example, in ET oxidation reactions, nanosecond laser-induced transient absorption measurements were performed to examine the fast ET from electron donors (e.g., ferrocene derivatives) to 2-Sc, affording a small reorganization energy (lambda = 0.26 eV) of ET, which is even much smaller than the lambda values reported in the ET reduction of heme Compound I (Cpd I) models and non-heme metal-oxo complexes. Such a small reorganization energy is ascribed to the TAML ligand centered ET reduction of 2-Sc. The lambda value of 0.26 eV was also obtained in the electron self-exchange reaction between 2-Sc and 1-Sc. In OAT reactions, the rate constants of the sulfoxidation of thioanisole derivatives by 2-Sc at -40 degrees C were much greater than those reported in the oxidation of thioanisoles by heme Cpd I and non-heme metal-oxo complexes. The reactivity of 2-Sc in hydrogen atom transfer (HAT) reactions is also discussed briefly. To the best of our knowledge, this Cr(V)-oxo TAML cation radical complex binding Sc3+ ion, {[Cr-V(O)(TAML(center dot+))]-Sc3+}(3+), with an extremely small reorganization energy is one of the most powerful high-valent metal-oxo oxidants in ET and OAT reactions.
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DOI
10.1021/acscatal.1c00079
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자연과학대학 > 화학·나노과학전공 > Journal papers
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