Angew Chem Int Ed Engl
Southern Laboratories-208A, Department of Chemistry, Indian Institute of Technology Kanpur, Kanpur, 208016, India.
Published: January 2024
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)(NO ) ] 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) results in the formation of (BnTPEN)Mn(IV)-O-Sc(III) (3), while HClO addition to 2 forms (BnTPEN)Mn(IV)-OH (4), reverting to 2 upon Ce(III)(NO ) addition. 2 can also be prepared by the oxidation of 1 eq. Ce(III)(NO ) with [(BnTPEN)Mn(IV)=O] (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.
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http://www.ncbi.nlm.nih.gov/pmc/articles/PMC10873046 | PMC |
http://dx.doi.org/10.1002/anie.202316378 | DOI Listing |
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