Back to Search
Start Over
Unprecedented pseudo-zeroth-order kinetics of the catecholase-like activity of mixed-valence MnIIMn2III complexes.
- Source :
-
New Journal of Chemistry . 5/28/2023, Vol. 47 Issue 20, p9681-9691. 11p. - Publication Year :
- 2023
-
Abstract
- During the past few decades, the synthesis of coordination complexes that exhibit high catalytic efficiencies has received significant attention from bio-inorganic chemists. In this context, two trinuclear mixed-valence manganese complexes, namely [MnIII2MnII(L1)2(OAc)4(H2O)2]·5H2O (1) and [MnIII2MnII(L2)2(OAc)4(CH3OH)2]·3CH3OH (2) [OAc = acetate] have been synthesized and structurally characterized. These complexes are shown to retain their nuclearity in acetonitrile medium, unveiling a new area of catecholase-like activity. In fact, both complexes showed an efficient oxidizing activity in acetonitrile using 3,5-di-tert-butylcatechol (3,5-DTBC) as the model substrate, and they were able to bring about complete oxidation of the substrate at a catalyst-to-substrate ratio of up to 1 : 600. To the best of our knowledge, the catecholase-like activity of trinuclear species is explored here for the first time. Interestingly, pseudo-zero-order kinetics with respect to the substrate are identified for both complexes, which represents the second report of this type of activity and the first report observed for a mixed-valence manganese complex. Details from experimental investigations of the mechanistic pathway revealed that the formation of oxygen radicals is believed to be the rate-limiting step, which supports the observation of the pseudo-zeroth-order kinetics. [ABSTRACT FROM AUTHOR]
- Subjects :
- *REACTIVE oxygen species
*CHEMISTS
*ACETONITRILE
*MANGANESE
Subjects
Details
- Language :
- English
- ISSN :
- 11440546
- Volume :
- 47
- Issue :
- 20
- Database :
- Academic Search Index
- Journal :
- New Journal of Chemistry
- Publication Type :
- Academic Journal
- Accession number :
- 163854798
- Full Text :
- https://doi.org/10.1039/d2nj06357c