Formation of a Reactive [Mn(III)−O−Ce(IV)] Species and its Facile Equilibrium with Related Mn(IV)(OX) (X = Sc or H) Complexes

Sikha Gupta, Pragya Arora, Rakesh Kumar, Ayushi Awasthi, Bittu Chandra, Raju Eerlapally, Jin Xiong, Yisong Guo, Lawrence Que, Apparao Draksharapu

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Lewis acid-bound high valent Mn-oxo species are of great importance due to their relevance to photosystem II. Here, we report the synthesis of a unique [(BnTPEN)Mn(III)−O−Ce(IV)(NO3)4]+ adduct (2) by the reaction of (BnTPEN)Mn(II) (1) with 4 eq. ceric ammonium nitrate. 2 has been characterized using UV/Vis, NMR, resonance Raman spectroscopy, as well as by mass spectrometry. Treatment of 2 with Sc(III)(OTf)3 results in the formation of (BnTPEN)Mn(IV)−O−Sc(III) (3), while HClO4 addition to 2 forms (BnTPEN)Mn(IV)−OH (4), reverting to 2 upon Ce(III)(NO3)3 addition. 2 can also be prepared by the oxidation of 1 eq. Ce(III)(NO3)3 with [(BnTPEN)Mn(IV)=O]2+ (5). In addition, the EPR spectroscopy revealed the elegant temperature-dependent equilibria between 2 and Mn(IV) species. The binding of redox-active Ce(IV) boosts electron transfer efficiency of 2 towards ferrocenes. Remarkably, the newly characterized Mn(III)−O−Ce(IV) species can carry out O-atom and H-atom transfer reactions.

Original languageEnglish (US)
Article numbere202316378
JournalAngewandte Chemie - International Edition
Issue number3
StatePublished - Jan 15 2024
Externally publishedYes

Bibliographical note

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  • Cerium
  • Electron Transfer
  • Manganese
  • Photosystem II
  • Redox-Active Lewis Acid

PubMed: MeSH publication types

  • Journal Article


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