期刊
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
卷 60, 期 12, 页码 6752-6756出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/anie.202015896
关键词
bioinorganic chemistry; enzyme models; high-valent iron; hydrogen atom abstraction; electron transfer
资金
- Deutsche Forschungsgemeinschaft (DFG, German Research Foundation) under Germany's Excellence Strategy [EXC 2008-390540038-UniSysCat]
- Heisenberg-Professorship
- MINECO [CTQ2017-87392-P]
- FEDER [UNGI10-4E-801]
- Einstein Foundation Berlin (ESB)-Einstein Center of Catalysis (EC2)
- Projekt DEAL
In this study, a novel S=2 oxoiron(IV) species supported by a unique ligand was generated and characterized. This species exhibited high reactivity in hydrogen atom abstraction reactions and demonstrated a unique oxidative mechanism. Complex 2 can serve as an excellent electronic and functional model for biological oxoiron(IV) intermediates.
S=2 oxoiron(IV) species act as reactive intermediates in the catalytic cycle of nonheme iron oxygenases. The few available synthetic S=2 Fe-IV=O complexes known to date are often limited to trigonal bipyramidal and very rarely to octahedral geometries. Herein we describe the generation and characterization of an S=2 pseudotetrahedral Fe-IV=O complex 2 supported by the sterically demanding 1,4,7-tri-tert-butyl-1,4,7-triazacyclononane ligand. Complex 2 is a very potent oxidant in hydrogen atom abstraction (HAA) reactions with large non-classical deuterium kinetic isotope effects, suggesting hydrogen tunneling contributions. For sterically encumbered substrates, direct HAA is impeded and an alternative oxidative asynchronous proton-coupled electron transfer mechanism prevails, which is unique within the nonheme oxoiron community. The high reactivity and the similar spectroscopic parameters make 2 one of the best electronic and functional models for a biological oxoiron(IV) intermediate of taurine dioxygenase (TauD-J).
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