Unique mononuclear MnII complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity
dc.contributor.author
dc.date.accessioned
2019-09-10T11:26:52Z
dc.date.available
2019-09-10T11:26:52Z
dc.date.issued
2016-07-04
dc.identifier.issn
1477-9226
dc.identifier.uri
dc.description.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
dc.format.mimetype
application/pdf
dc.language.iso
eng
dc.publisher
Royal Society of Chemistry
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Reproducció digital del document publicat a: https://doi.org/10.1039/C6DT00625F
dc.relation.ispartof
Dalton Transactions, 2016, vol. 45, p. 12409-12422
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Articles publicats (D-Q)
dc.rights
Attribution-NonCommercial 4.0 International
dc.rights.uri
dc.subject
dc.title
Unique mononuclear MnII complexes of an end-off compartmental Schiff base ligand: experimental and theoretical studies on their bio-relevant catalytic promiscuity
dc.type
info:eu-repo/semantics/article
dc.rights.accessRights
info:eu-repo/semantics/openAccess
dc.type.version
info:eu-repo/semantics/publishedVersion
dc.identifier.doi
dc.identifier.idgrec
026294
dc.type.peerreviewed
peer-reviewed
dc.identifier.eissn
1477-9234