Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand.
A copper(II)-hydroperoxo complex, [Cu(Me(6)-tren)(OOH)](+) (2), and a copper(ii)-cumylperoxo complex, [Cu(Me(6)-tren)(OOC(CH(3))(2)Ph)](+) (3), were synthesized by reacting [Cu(Me(6)-tren)(CH(3)CN)](2+) (1) with H(2)O(2) and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)-OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configurations of 2 and 3, showing trigonal bipyramidal copper(II)-OOR geometries. These copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.
Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea.
Yu Jin
YJ
Choi
Kyung-Bin
KB
Cho
Minoru
M
Kubo
Takashi
T
Ogura
Kenneth D
KD
Karlin
Jaeheung
J
Cho
Wonwoo
W
Nam
D001555:Benzene Derivatives / Q000737:chemistry*; D056831:Coordination Complexes / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D008024:Ligands; D008968:Molecular Conformation; D013056:Spectrophotometry, Ultraviolet; D013059:Spectrum Analysis, Raman
D001555:Benzene Derivatives; D056831:Coordination Complexes; D008024:Ligands; D003300:Copper; C007164:cumene hydroperoxide
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