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Redox chemistry of a dimanganese(II,III) complex with an unsymmetric ligand: Water binding, deprotonation and accumulative light-induced oxidation
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för fotokemi och molekylärvetenskap.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för fotokemi och molekylärvetenskap.
Uppsala universitet, Teknisk-naturvetenskapliga vetenskapsområdet, Kemiska sektionen, Institutionen för fotokemi och molekylärvetenskap.
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2006 (engelsk)Inngår i: European Journal of Inorganic Chemistry, ISSN 1434-1948, E-ISSN 1099-1948, nr 24, s. 5033-5047Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

A dinuclear manganese complex {[(Mn2L)-L-II,IIII(mu-OAc)(2)]-ClO4} has been synthesised, where L is the dianion of 2-{[bis-(pyrid-2-ylmethyl)amino]methyl}-6-{[(3,5-di-tert-butyl-2- hydroxybenzyl)(pyrid-2-ylmethyl)amino]methyl)-4-methylphenol, an unsymmetric binucleating ligand with two coordinating phenol groups. The two manganese ions, with a Mn-Mn distance of 3.498 angstrom, are bridged by the two bidentate acetate ligands and the 4-methylphenolate group of the ligand, resulting in a N3O3 and N2O4 donor set of Mn-II and Mn-II, respectively. Electrochemically [Mn2(II,III)L(mu-OAc)(2)](+) is reduced to [(Mn2L)-L-II,II(mu-OAc)(2)] at E-1/2(1)=-0.53 V versus Fc(+/0) and oxidised to [(Mn2L)-L-III,III(mu-OAC)(2)](2+) at E-1/2(2)=0.38 V versus Fc(+/0). All three redox states have been characterised by EPR, IR and UV/Vis spectroscopy. Subsequent oxidation of [(Mn2L)-L-II,III(mu-OAc)(2)](2+) [E-1/2(3)=0.75 V vs. Fc(+/0)] in dry acetonitrile results in an unstable primary product with a lifetime of about 100 ins. At high scan rates quasireversible voltammetric behaviour is found for all three electrode processes, with particularly slow electron transfer for the II,III/II,II [k(o)(1) = 0.002 cms(-1) and III,III/II,III [k(o)(2) = 0.005 cms(-1)] couples, which can be rationalised in terms of major distortions of the Mn-II centres. In aqueous media the bridging acetates are replaced by water-derived ligands. Deprotonation of these stabilises higher valence states, and photo-induced oxidation of the manganese complex results in a (Mn2L)-L-IlI,IV complex with oxo or hydroxo bridging ligands, which is further oxidised to an EPR-silent product. These results demonstrate that a larger number of metal-centred oxidations can be compressed in a narrow potential range if build up of charge is avoided by charge-compensating reactions.

sted, utgiver, år, opplag, sider
2006. nr 24, s. 5033-5047
Emneord [en]
manganese, bioinorganic chemistry, ligand exchange, EPR spectroscopy, IR spectroscopy
HSV kategori
Identifikatorer
URN: urn:nbn:se:uu:diva-146660DOI: 10.1002/ejic.200600676ISI: 000243077800009OAI: oai:DiVA.org:uu-146660DiVA, id: diva2:398674
Tilgjengelig fra: 2011-02-18 Laget: 2011-02-18 Sist oppdatert: 2017-12-11

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