Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear CoIV–Dinitrate Complex
Abstract
High-valent FeIV=O intermediates with a terminal metal–oxo moiety are key oxidants in many enzymatic and synthetic C–H bond oxidation reactions. While generating stable metal–oxo species for late transition metals remains synthetically challenging, notably, a number of high-valent non-oxo–metal species of late transition metals have been recently described as strong oxidants that activate C–H bonds. In this work, we obtained an unprecedented mononuclear CoIV–dinitrate complex (2) upon one-electron oxidation of its Co(III) precursor supported by a tridentate dianionic N3 ligand. 2 was structurally characterized by X-ray crystallography, showing a square pyramidal geometry with two coordinated nitrate anions. Furthermore, characterization of 2 using combined spectroscopic and computational methods revealed that 2 is a low-spin (S = 1/2) Co(IV) species with the unpaired electron located on the cobalt dz2 orbital, which is well positioned for substrate oxidations. Indeed, while having a high thermal stability, 2 is able to cleave sp3 C–H bonds up to 87 kcal/mol to afford rate constants and kinetic isotope effects (KIEs) of 2–6 that are comparable to other high-valent metal oxidants. The ability to oxidize strong C–H bonds has yet to be observed for CoIV–O and CoIII=O species previously reported. Therefore, 2 represents the first high-valent Co(IV) species thatmore »
- Authors:
-
[1];
[2];
[1];
[2];
[1]
- Univ. of Montana, Missoula, MT (United States). Dept. of Chemistry and Biochemistry. Center for Biomolecular Structure and Dynamics
- Univ. of Kansas, Lawrence, KS (United States). Dept. of Chemistry. Center for Environmentally Beneficial Catalysis
- Publication Date:
- Research Org.:
- Univ. of Kansas, Lawrence, KS (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1802949
- Grant/Contract Number:
- SC0016359
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 142; Journal Issue: 31; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; anions; ligands; crystal structure; electron paramagnetic resonance spectroscopy; oxidation
Citation Formats
Kwon, Yubin M., Lee, Yuri, Evenson, Garrett E., Jackson, Timothy A., and Wang, Dong. Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear CoIV–Dinitrate Complex. United States: N. p., 2020.
Web. doi:10.1021/jacs.0c04368.
Kwon, Yubin M., Lee, Yuri, Evenson, Garrett E., Jackson, Timothy A., & Wang, Dong. Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear CoIV–Dinitrate Complex. United States. https://doi.org/10.1021/jacs.0c04368
Kwon, Yubin M., Lee, Yuri, Evenson, Garrett E., Jackson, Timothy A., and Wang, Dong. Wed .
"Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear CoIV–Dinitrate Complex". United States. https://doi.org/10.1021/jacs.0c04368. https://www.osti.gov/servlets/purl/1802949.
@article{osti_1802949,
title = {Crystal Structure and C–H Bond-Cleaving Reactivity of a Mononuclear CoIV–Dinitrate Complex},
author = {Kwon, Yubin M. and Lee, Yuri and Evenson, Garrett E. and Jackson, Timothy A. and Wang, Dong},
abstractNote = {High-valent FeIV=O intermediates with a terminal metal–oxo moiety are key oxidants in many enzymatic and synthetic C–H bond oxidation reactions. While generating stable metal–oxo species for late transition metals remains synthetically challenging, notably, a number of high-valent non-oxo–metal species of late transition metals have been recently described as strong oxidants that activate C–H bonds. In this work, we obtained an unprecedented mononuclear CoIV–dinitrate complex (2) upon one-electron oxidation of its Co(III) precursor supported by a tridentate dianionic N3 ligand. 2 was structurally characterized by X-ray crystallography, showing a square pyramidal geometry with two coordinated nitrate anions. Furthermore, characterization of 2 using combined spectroscopic and computational methods revealed that 2 is a low-spin (S = 1/2) Co(IV) species with the unpaired electron located on the cobalt dz2 orbital, which is well positioned for substrate oxidations. Indeed, while having a high thermal stability, 2 is able to cleave sp3 C–H bonds up to 87 kcal/mol to afford rate constants and kinetic isotope effects (KIEs) of 2–6 that are comparable to other high-valent metal oxidants. The ability to oxidize strong C–H bonds has yet to be observed for CoIV–O and CoIII=O species previously reported. Therefore, 2 represents the first high-valent Co(IV) species that is both structurally characterized by X-ray crystallography and capable of activating strong C–H bonds.},
doi = {10.1021/jacs.0c04368},
journal = {Journal of the American Chemical Society},
number = 31,
volume = 142,
place = {United States},
year = {Wed Jul 08 00:00:00 EDT 2020},
month = {Wed Jul 08 00:00:00 EDT 2020}
}
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