Structural and Spectroscopic Characterization of Metastable Thiolate-Ligated Manganese(III)–Alkylperoxo Species
Citations Over TimeTop 10% of 2011 papers
Abstract
Metastable Mn-peroxo species are proposed to form as key intermediates in biological oxidation reactions involving O(2) and C-H bond activation. The majority of these have yet to be spectroscopically characterized, and their inherent instability, in most cases, precludes structural characterization. Cysteinate-ligated metal-peroxos have been shown to form as reactive intermediates in both heme and nonheme iron enzymes. Herein we report the only examples of isolable Mn(III)-alkylperoxo species, and the first two examples of structurally characterized synthetic thiolate-ligated metal-peroxos. Spectroscopic data, including electronic absorption and IR spectra, and ESI mass spectra for (16)O vs (18)O-labeled metastable Mn(III)-OOR (R = (t)Bu, Cm) are discussed, as well as preliminary reactivity.
Related Papers
- → Electrogenerated Cationic Reactive Intermediates: The Pool Method and Further Advances(2017)547 cited
- → Oxidizing Intermediates in P450 Catalysis: A Case for Multiple Oxidants(2015)33 cited
- → Direct mass spectrometric observation and reaction mechanism of gas-phase initial intermediates during CL-20 decomposition(2022)20 cited
- → Introduction(1992)