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dc.contributor.author Kim, Bohee ko
dc.contributor.author Kim, Seonghan ko
dc.contributor.author Ohta, Takehiro ko
dc.contributor.author Cho, Jaeheung ko
dc.date.accessioned 2021-01-22T07:37:37Z -
dc.date.available 2021-01-22T07:37:37Z -
dc.date.created 2020-07-30 -
dc.date.created 2020-07-30 -
dc.date.issued 2020-07 -
dc.identifier.citation Inorganic Chemistry, v.59, no.14, pp.9938 - 9943 -
dc.identifier.issn 0020-1669 -
dc.identifier.uri http://hdl.handle.net/20.500.11750/12817 -
dc.description.abstract The importance of redox-inactive metal ions in modulating the reactivity of redox-active biological systems is a subject of great current interest. In this work, the effect of redox-inactive metal ions (M3+ = Sc3+, Y3+, Yb3+, La3+) on the nucleophilic reactivity of a mononuclear ligand-based alkylperoxocopper(II) complex, [Cu(iPr2-tren-C(CH3)2O2)]+ (1), was examined. 1 was prepared by the addition of hydrogen peroxide and triethylamine to the solution of [Cu(iPr3-tren)(CH3CN)]+ (iPr3-tren = tris[2-(isopropylamino)ethyl]amine) via the formation of [Cu(iPr3-tren)(O2H)]+ (2) in methanol (CH3OH) at 30 °C. 1 was characterized using density functional theory (DFT) calculations and spectroscopic methods such as UV-vis, resonance Raman (rR), and electron paramagnetic resonance (EPR). DFT calculations support the electronic structure of 1 with an intermediate geometry between the trigonal-bipyramidal and square-pyramidal geometries, which is consistent with the observed EPR signal exhibiting a signal with g⊥ = 2.03 (A⊥ = 16 G) and g|| = 2.19 (A|| = 158 G). The Cu-O bond stretching frequency of 1 was observed at 507 cm-1 for 16O2 species (486 cm-1 for 18O2 species), and its O-O vibrational energy was determined to be 799 cm-1 for 16O2 species (759 cm-1 for 18O2 species) by rR spectroscopy. The reactivity of 1 was investigated in oxidative nucleophilic reactions. The positive slope of the Hammett plot (ρ = 2.3(1)) with para-substituted benzaldehydes and the reactivity order with 1°-, 2°-, and 3°-CHO demonstrate well the nucleophilic character of this copper(II) ligand-based alkylperoxo complex. The Lewis acidity of M3+ improves the oxidizing ability of 1. The modulated reactivity of 1 with M3+ was revealed to be an opposite trend of the Lewis acidity of M3+ in aldehyde deformylation. © 2020 American Chemical Society. -
dc.language English -
dc.publisher American Chemical Society -
dc.title Redox-Inactive Metal Ions That Enhance the Nucleophilic Reactivity of an Alkylperoxocopper(II) Complex -
dc.type Article -
dc.identifier.doi 10.1021/acs.inorgchem.0c01109 -
dc.identifier.wosid 000552287100047 -
dc.identifier.scopusid 2-s2.0-85088121410 -
dc.type.local Article(Overseas) -
dc.type.rims ART -
dc.description.journalClass 1 -
dc.contributor.localauthor Cho, Jaeheung -
dc.contributor.nonIdAuthor Ohta, Takehiro -
dc.identifier.citationVolume 59 -
dc.identifier.citationNumber 14 -
dc.identifier.citationStartPage 9938 -
dc.identifier.citationEndPage 9943 -
dc.identifier.citationTitle Inorganic Chemistry -
dc.type.journalArticle Article -
dc.description.isOpenAccess N -

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