Active catalytic centers in silica-supported Cu(II) and Mn(II) biomimetic complexes: Correlation between catalytic and EPR data

Simple item page
dc.contributor.authorZois, D.en
dc.contributor.authorVartzouma, C.en
dc.contributor.authorDeligiannakis, Y.en
dc.contributor.authorHadjiliadis, N.en
dc.contributor.authorCasella, L.en
dc.contributor.authorMonzani, E.en
dc.contributor.authorLouloudi, M.en
dc.date.accessioned2015-11-24T16:42:56Z
dc.date.available2015-11-24T16:42:56Z
dc.identifier.issn1381-1169-
dc.identifier.urihttps://olympias.lib.uoi.gr/jspui/handle/123456789/8621
dc.rightsDefault Licence-
dc.subjectsupported complexesen
dc.subjectcopper and manganese complexesen
dc.subjectbiomimetic catalysisen
dc.subjectepr and hyscore spectraen
dc.subjectalkene epoxidationen
dc.subjectcatechol oxidationen
dc.subjectdtbqen
dc.subjectelectron-spin-resonanceen
dc.subjectenantioselective epoxidation catalystsen
dc.subjectcatechol oxidase activityen
dc.subjectdinuclear copper complexen
dc.subjectmanganese porphyrinsen
dc.subjectunpaired electronsen
dc.subjectinterspin distanceen
dc.subjecthydrogen-peroxideen
dc.subjectoxidationen
dc.subjectspectroscopyen
dc.titleActive catalytic centers in silica-supported Cu(II) and Mn(II) biomimetic complexes: Correlation between catalytic and EPR dataen
heal.abstractTwo polydentate ligands represented as L-A and L-B have been synthesized and subsequently grafted on a silica surface via covalent bonds. The organic ligands LA and LB as well as the heterogenized ligands (LASiO2)-Si-. and L-B .SiO2 reacted with manganese(II) and copper(II) ions leading to the formation of the corresponding metal complexes. Catalytic epoxidations of simple olefins with hydrogen peroxide were studied using the above manganese complexes in the presence of a cocatalyst. The major products of the oxidations were the epoxides and the studied manganese complexes showed significant catalytic activities. The copper(II) complexes have been evaluated for the catalytic oxidation of 3,5-di-t-butylcatechol (DTBC) by dioxygen. Based on a combination of structural information, obtained form EPR spectroscopy, and the catalytic activity we suggest that the catalysis of DTBC oxidation by copper complexes is critically determined by two factors (a) for dinuclear complexes, it is enhanced when the (CuCu)-Cu-... distance approaches the (OCCO)-C-... distance in the catechol molecule (2.7 angstrom), and (b) immobilization on silica support results in enhancement of the catalytic activity in cases where even monomeric complexes are located at relative distances approaching the critical (OCCO)-C-... distance (2.7 angstrom). This provides a practical rule for design and synthesis of more efficient copper-catalysts for the catechol oxidation. (c) 2006 Elsevier B.V. All rights reserved.en
heal.accesscampus-
heal.fullTextAvailabilityTRUE-
heal.identifier.primaryDOI 10.1016/j.molcata.2006.11.023-
heal.identifier.secondary<Go to ISI>://000243561000027-
heal.identifier.secondaryhttp://ac.els-cdn.com/S1381116906013811/1-s2.0-S1381116906013811-main.pdf?_tid=f7057cc4-362e-11e3-8e39-00000aacb360&acdnat=1381906289_428405f2aca9adeccbaecc4e500880f0-
heal.journalNameJournal of Molecular Catalysis a-Chemicalen
heal.journalTypepeer reviewed-
heal.languageen-
heal.publicationDate2007-
heal.publisherElsevieren
heal.recordProviderΠανεπιστήμιο Ιωαννίνων. Σχολή Θετικών Επιστημών. Τμήμα Χημείαςel
heal.typejournalArticle-
heal.type.elΆρθρο Περιοδικούel
heal.type.enJournal articleen

Files

License bundle

Now showing 1 - 1 of 1
Thumbnail Image
Name:
license.txt
Size:
1.74 KB
Format:
Item-specific license agreed upon to submission
Description:
Download

Collections

Άρθρα σε επιστημονικά περιοδικά ( Ανοικτά). ΧΗΜ