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Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
Exploring the nitric oxide dioxygenation (NOD) reactions of manganese-peroxo complexes
Sandip Das1, Akshaya Keerthi C S1, Kulbir1
1Department of Chemistry, Indian Institute of Science Education and Research (IISER), Tirupati 517507, India. pankajatiisert@gmail.com.
Abstract:
Here, we report the nitric oxide dioxygenation (NOD) reactions of two MnIII-peroxo (MIII-O22-) complexes, [(3PYENMe)MnIII(O22-)]+ (1) and [(N3PY)MnIII(O22-)]+ (2), bearing pentadentate ligands. Complexes 1 and 2 give MnII-nitrate (MnII-NO3-) complexes (3 and 4) when reacted with nitric oxide (NO), respectively. The mechanistic study explored by using 2,4-di-tert-butylphenol (2,4-DTBP) suggested that the NOD reaction of 1 and 2 occurs via a presumed Mn-peroxynitrite ([Mn-PN]+, [Mn-ONOO-]+) intermediate. Tracking the source of N atoms using 15NO revealed that the N-atoms in MnII-NO3- (3 and 4) are derived from the 15NO moiety. Furthermore, we have explored the MIII-O22- regeneration from NOD products (3 and 4), and we have observed the formation of MIII-O22- complexes (1 and 2) upon treatment with KO2 or H2O2/triethylamine (TEA), respectively.
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