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• W2603933624 endingPage "4681" @default.
• W2603933624 startingPage "4675" @default.
• W2603933624 abstract "The molecular mechanism of the Oxygen Evolving Center of photosystem II has been under debate for decades. One frequently cited proposal is the nucleophilic attack by water hydroxide on a pendant Mn═O moiety, though no chemical example of this reactivity at a manganese cubane cluster has been reported. We describe here the preparation, characterization, and a reactivity study of a synthetic manganese cubane cluster with a pendant manganese-oxo moiety. Reaction of this cluster with alkenes results in oxygen and hydrogen atom transfer reactions to form alcohol- and ketone-based oxygen-containing products. Nitrene transfer from core imides is negligible. The inorganic product is a cluster identical to the precursor, but with the pendant Mn═O moiety replaced by a hydrogen abstracted from the organic substrate, and is isolated in quantitative yield. 18O and 2H isotopic labeling studies confirm the transfer of atoms between the cluster and the organic substrate. The results suggest that the core cubane structure of this model compound remains intact, and that the pendant Mn═O moiety is preferentially reactive." @default.
• W2603933624 created "2017-04-07" @default.
• W2603933624 creator A5045633562 @default.
• W2603933624 creator A5055284513 @default.
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• W2603933624 creator A5070540199 @default.
• W2603933624 creator A5075743520 @default.
• W2603933624 creator A5076246398 @default.
• W2603933624 date "2017-03-24" @default.
• W2603933624 modified "2023-09-26" @default.
• W2603933624 title "Reactive Pendant Mn═O in a Synthetic Structural Model of a Proposed S₄ State in the Photosynthetic Oxygen Evolving Complex" @default.
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• W2603933624 doi "https://doi.org/10.1021/jacs.6b05906" @default.
• W2603933624 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/28288514" @default.
• W2603933624 hasPublicationYear "2017" @default.
• W2603933624 type Work @default.

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