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Oxalate Oxidase Model Studies – Substrate Reactivity
Author(s) -
Pawlak Piotr L.,
Panda Manashi,
Li Jia,
Banerjee Atanu,
Averill Derek J.,
Nikolovski Borislava,
Shay Brian J.,
Brennessel William W.,
Chavez Ferman A.
Publication year - 2015
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402835
Subject(s) - chemistry , oxalate , carboxylate , ligand (biochemistry) , oxalic acid , inorganic chemistry , reactivity (psychology) , medicinal chemistry , electron paramagnetic resonance , ion , stereochemistry , organic chemistry , medicine , biochemistry , physics , receptor , alternative medicine , pathology , nuclear magnetic resonance
The synthesis and structure of [MnLCl]0.5H 2 O ( 1· 0.5H 2 O, HL = 1‐benzyl‐4‐acetato‐1,4,7‐triazacyclononane) is reported. Complex 1 exists as a coordination polymer in the solid state, and the Mn II center is bonded to three amine nitrogen atoms, one carboxylate oxygen atom, a chlorido ligand, and an adjacent carboxylate group in a chelating fashion to afford a seven‐coordinate center. The dissolution of 1 in acetonitrile containing excess oxalate (ox) ions results in a monomeric species. When mixtures of 1 and oxalate ions are exposed to oxygen under ambient conditions, a dark pink EPR‐silent species is generated. The pink species is believed to be [Mn III (ox) 2 ] – , which results from the displacement of the ligand L – by an oxalate ion. The decomposition of this species ultimately results in the formation of 1 equiv. of CO 2 per oxalate ion consumed, a HCO 3 – ion, and a Mn II species. Further reaction of the resulting Mn II species with excess oxalate in the presence of oxygen leads to additional oxalate degradation.