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Unique mononuclear MnIIcomplexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity
Published in Royal Society of Chemistry (RSC)
Volume: 45
Issue: 31
Pages: 12409 - 12422

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- Page 1 of 35 Dalton Transactions Dalton Transactions Accepted Manuscript Published on 04 July 2016. Downloaded by University of Sussex on 04/07/2016 11:50:52. View Article Online DOI: 10.1039/C6DT00625F 2 pyridin-2-yl-ethylimino)-methyl]-phenol] have been synthesized and structurally characterized. “End-Off” compartmental ligand (LH) possesses two symmetrical compartments with N2O binding sites but accommodates only one manganese atom instead of two due to protonation of imine nitrogen of one compartment. Although all three complexes are mononuclear, complex 1 is unique as it has 1:2 metal to ligand stoichiometry. Catalytic promiscuity of complexes 1-3 in terms of two different bio-relevant catalytic activities namely catecholase and phenoxazinone synthase have 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. Computational approach suggests that imine bond bound radical generation rather than phenoxo radical formation is most likely responsible for oxidizing property of the complexes.

About the journal
JournalData powered by TypesetDalton Transactions
PublisherData powered by TypesetRoyal Society of Chemistry (RSC)
Open AccessNo