Journal
ACS CATALYSIS
Volume 11, Issue 5, Pages 2889-2901Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acscatal.1c00079
Keywords
electron transfer; oxygen atom transfer; chromium(V)-oxo complex; redox-inactive metal ion; reorganization energy
Categories
Funding
- NRF of Korea through CRI [NRF-2012R1A3A2048842]
- Basic Science Research Program [2020R1I1A1A01074630, 2019R1I1A1A01055822, 2020R1A6A3A13072451]
- NSF [CHE-1900476]
- Xi'an Key Laboratory of Organometallic Material Chemistry
- U.S. DOE [DE-AC02-06CH11357]
- U.S. Department of Energy, Basic Energy Science
- Canadian Light Source
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The synthesis, characterization, and electron-transfer oxidation reactivity of a chromium(V)-oxo TAML cation radical complex binding Sc3+ ion were reported. The complex demonstrated highly reactive oxidizing capability with an extremely small reorganization energy, making it one of the most powerful high-valent metal-oxo oxidants in ET and OAT reactions.
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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