410527-33-2Relevant academic research and scientific papers
Dioxygen activation at a single copper site: Structure, bonding, and mechanism of formation of 1:1 Cu-O2 adducts
Aboelella, Nermeen W.,Kryatov, Sergey V.,Gherman, Benjamin F.,Brennessel, William W.,Young Jr., Victor G.,Sarangi, Ritimukta,Rybak-Akimova, Elena V.,Hodgson, Keith O.,Hedman, Britt,Solomon, Edward I.,Cramer, Christopher J.,Tolman, William B.
, p. 16896 - 16911 (2007/10/03)
To evaluate the fundamental process of O2 activation at a single copper site that occurs in biological and catalytic systems, a detailed study of O2 binding to Cu(I) complexes of β-diketiminate ligands L (L1 = backbone Me; L2 = backbone tBu) by X-ray crystallography, X-ray absorption spectroscopy (XAS), cryogenic stopped-flow kinetics, and theoretical calculations was performed. Using synchrotron radiation, an X-ray diffraction data set for L2CuO2 was acquired, which led to structural parameters in close agreement to theoretical predictions. Significant Cu(III) - peroxo character for the complex was corroborated by XAS. On the basis of stopped-flow kinetics data and theoretical calculations for the oxygenation of L1Cu(RCN) (R = alkyl, aryl) in THF and THF/RCN mixtures between 193 and 233 K, a dual pathway mechanism is proposed involving (a) rate-determining solvolysis of RCN by THF followed by rapid oxygenation of L1Cu(THF) and (b) direct, bimolecular oxygenation of L1Cu(RCN) via an associative process.
β-diketiminate ligand backbone structural effects on Cu(I)/O2 reactivity: Unique copper-superoxo and Bis(μ-oxo) complexes
Spencer, Douglas J.E.,Aboelella, Nermeen W.,Reynolds, Anne M.,Holland, Patrick L.,Tolman, William B.
, p. 2108 - 2109 (2007/10/03)
Copper(I) and -(II) complexes of β-diketiminate ligands with identical flanking 2,6-diisopropylphenyl groups but divergent backbone substitution patterns were prepared and structurally characterized, and reactions of the Cu(I) species with O2 a
