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Redox-Inactive Metal Ions That Enhance the Nucleophilic Reactivity of an Alkylperoxocopper(II) Complex

Title
Redox-Inactive Metal Ions That Enhance the Nucleophilic Reactivity of an Alkylperoxocopper(II) Complex
Authors
Kim, BoheeKim, SeonghanOhta, TakehiroCho, Jaeheung
DGIST Authors
Cho, Jaeheung
Issue Date
2020-07
Citation
Inorganic Chemistry, 59(14), 9938-9943
Type
Article
Article Type
Article
ISSN
0020-1669
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.
URI
http://hdl.handle.net/20.500.11750/12817
DOI
10.1021/acs.inorgchem.0c01109
Publisher
American Chemical Society
Files:
There are no files associated with this item.
Collection:
Department of Emerging Materials ScienceBiomimetic Materials Laboratory1. Journal Articles


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