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Issue 31, 2016
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Unique mononuclear MnII complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity

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Abstract

Three new mononuclear manganese(II) complexes, namely [Mn(HL)2]·2ClO4 (1), [Mn(HL)(N(CN)2)(H2O)2]·ClO4 (2) and [Mn(HL)(SCN)2] (3) [LH = 4-tert-butyl-2,6-bis-[(2-pyridin-2-yl-ethylimino)-methyl]-phenol], have been synthesized and structurally characterized. An “end-off” compartmental ligand (LH) possesses two symmetrical compartments with N2O binding sites but accommodates only one manganese atom instead of two due to the protonation of the imine nitrogen of one compartment. Although all three complexes are mononuclear, complex 1 is unique as it has a 1 : 2 metal to ligand stoichiometry. The catalytic promiscuity of complexes 1–3 in terms of two different bio-relevant catalytic activities namely catecholase and phenoxazinone synthase has been thoroughly investigated. EPR and cyclic voltametric studies reveal that radical formation rather than metal centered redox participation is responsible for their catecholase-like and phenoxazinone synthase-like catalytic activity. A computational approach suggests that imine bond bound radical generation rather than phenoxo radical formation is most likely responsible for the oxidizing properties of the complexes.

Graphical abstract: Unique mononuclear MnII complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity

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Publication details

The article was received on 16 Feb 2016, accepted on 01 Jul 2016 and first published on 04 Jul 2016


Article type: Paper
DOI: 10.1039/C6DT00625F
Citation: Dalton Trans., 2016,45, 12409-12422
  • Open access: Creative Commons BY-NC license
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    Unique mononuclear MnII complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity

    J. Adhikary, A. Chakraborty, S. Dasgupta, S. K. Chattopadhyay, R. Kruszynski, A. Trzesowska-Kruszynska, S. Stepanović, M. Gruden-Pavlović, M. Swart and D. Das, Dalton Trans., 2016, 45, 12409
    DOI: 10.1039/C6DT00625F

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