Spectroscopic and theoretical studies of an end-on peroxide-bridged coupled binuclear copper(II) model complex of relevance to the active sites in hemocyanin and tyrosinase

• Published in: Journal of the American Chemical Society Vol. 113; no. 23; pp. 8671 - 8679
• Main Authors: Baldwin, Michael J, Ross, Paul K, Pate, James E, Tyeklar, Zoltan, Karlin, Kenneth D, Solomon, Edward I
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 01.11.1991
• Subjects: Atomic and molecular physics; binding; chemical properties; copper; Exact sciences and technology; hemocyanin; Molecular properties and interactions with photons; monophenol monooxygenase; Physics; Properties of molecules and molecular ions; Chemical solution; Resonance state; Enzyme; Active site; Theoretical study; Transition metal Complexes; Experimental study; Calculating method; Absorption spectrum; Intramolecular charge transfer; Inorganic compound; Electronic structure; Vibrational analysis; Copper II Complexes; Dimer; Raman spectrum; Intramolecular interaction
• ISSN: 0002-7863; 1520-5126
• DOI: 10.1021/ja00023a014

Spectroscopic studies have been combined with broken-symmetry SCF-X alpha -SW calculations to determine the vibrational and electronic structure of peroxide-copper bonding in the end-on trans mu -1,2 peroxide-bridged copper dimer, ((Cu(TMPA)) sub(2) (O sub(2))) super(2+). This study provides a detailed understanding of the electronic structure generally associated with an end-on peroxide-bridging mode and additionally shows important dimer interactions which are not present in the copper-peroxide monomer.