期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 40, 页码 15874-15877出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja2066237
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资金
- NSF [CHE0909587]
- Harry and Cleio Greer Fellowship
- University of Manchester
- Engineering and Physical Sciences Research Council [EP/J003921/1] Funding Source: researchfish
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0909587] Funding Source: National Science Foundation
- EPSRC [EP/J003921/1] Funding Source: UKRI
One-electron oxidation of Mn-v-oxo corrolazine 2 affords 2(+), the first example of a Mn-v(O) pi-cation radical porphyrinoid complex, which was characterized by UV-vis, EPR, LDI-MS, and DFT methods. Access to 2 and 2(+) allowed for a direct comparison of their reactivities in oxygen-atom transfer (OAT) reactions. Both complexes are capable of OAT to PPh3 and RSR substrates, and 2(+) was found to be a more potent oxidant than 2. Analysis of rate constants and activation parameters, together with DFT calculations, points to a concerted OAT mechanism for 2(+) and 2 and indicates that the greater electrophilicity of 2(+) likely plays a dominant role in enhancing its reactivity. These results are relevant to comparisons between Compound I and Compound II in heme enzymes.
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