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Synthesis and characterization of a dinuclear manganese(III,III) complex with three phenolate ligands
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2002 (English)In: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-0682, no 11, 2965-2974 p.Article in journal (Refereed) Published
Abstract [en]

A dinuclear manganese complex ([Mn2L(mu-OAc)(2)]PF6) has been synthesized, where L is the trianion of 2,6-bis{[(2-hydroxy-3,5-di- tert-butylbenzyl) (2-pyridylmethyl) amino] methyl)-4-methylphenol, a ligand with three phenolate groups. The two pseudo-octahedrally coordinated Mn ions are bridged via the two bidentate acetate ligands and the 4-methylphenolate group of the ligand. We have characterized the complex with electrochemistry, spectroelectrochemistry and EPR spectroscopy. Electrochemically the Mn-2(III,III) complex undergoes two metal-centered quasi-reversible one-electron reduction steps (E-1/2 = 0.04 and -0.32 V vs. SCE). Reduction to the Mn-2(II,III) state results in transformation into a modified complex with slightly different redox properties. One-electron oxidation (E-1/2 = 0.96 V vs. SCE) affords the Mn-2(III,IV) state while further one-electron oxidation (E-1/2 = 1.13 V vs. SCE) presumably involves ligand oxidation. High valent Mn complexes involving Mn-IV or Mn-V centers are of particular interest as intermediates in catalytic water oxidation. The redox potentials of [Mn2L(mu-OAC)(2)](+) show the expected stabilization of higher manganese oxidation states compared with the related complex, [Mn-2(bpmp)(mu-OAc)(2)](+).

Place, publisher, year, edition, pages
2002. no 11, 2965-2974 p.
Keyword [en]
manganese, ligand design, redox chemistry, valence mniimniii complexes, water-oxidation, photosystem-ii, copper(ii) complexes, metal-complexes, photosynthesis, cluster, models, dimer, redox
URN: urn:nbn:se:kth:diva-22001ISI: 000178876500029OAI: diva2:340699
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

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