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Title: A High‐Valent Manganese(IV)–Oxo–Cerium(IV) Complex and Its Enhanced Oxidizing Reactivity
Abstract

A mononuclear nonheme manganese(IV)–oxo complex binding the Ce4+ion, [(dpaq)MnIV(O)]+–Ce4+(1‐Ce4+), was synthesized by reacting [(dpaq)MnIII(OH)]+(2) with cerium ammonium nitrate (CAN).1‐Ce4+was characterized using various spectroscopic techniques, such as UV/Vis, EPR, CSI‐MS, resonance Raman, XANES, and EXAFS, showing an Mn−O bond distance of 1.69 Å with a resonance Raman band at 675 cm−1. Electron‐transfer and oxygen atom transfer reactivities of1‐Ce4+were found to be greater than those of MnIV(O) intermediates binding redox‐inactive metal ions (1‐Mn+). This study reports the first example of a redox‐active Ce4+ion‐bound MnIV‐oxo complex and its spectroscopic characterization and chemical properties.

 
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Award ID(s):
1900476
NSF-PAR ID:
10118060
Author(s) / Creator(s):
 ;  ;  ;  ;  ;  ;  ;  ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
58
Issue:
45
ISSN:
1433-7851
Page Range / eLocation ID:
p. 16124-16129
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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