title: Enzyme-mimetic model compounds: conformational analysis and far-IR study of Cu(TAAB)2+.
abstract: Many enzymes occurring in nature like superoxide dismutase are systems rather too big to be accessible for vibrational and quantum chemical investigations. Thus, enzyme-mimetic model compounds consisting of a biological active metal centre surrounded by a macrocyclic ligand are used to shed light on binding properties of the active metal centre. Far- and mid-range IR spectroscopic investigations and a conformational analysis with the semi-empirical ZINDO/1 method of superoxide dismutase-mimetic complex Cu[TAAB]2+ are performed (TAAB = [b,f,j,n][1,5,9,13]tetra-aza-cyclohexadecine (tetra-anhydroamino benzaldehyde)). A distorted tetrahedral copper(II) centre with slightly twisted phenyl subunits is determined as the most stable conformation. Calculated mid- and far-IR spectra are in good agreement with the experimental data and confirm the proposed structure. A harmonic normal-coordinate analysis is used to assign the vibrational modes of the observed spectra.
authors.affiliation: Institute for Inorganic Chemistry, Vienna University of Technology, Austria. weinberg@mail.zserv.tuwien.ac.at
authors.forename: P
authors.initials: P
authors.lastname: Weinberger
authors.forename: R
authors.initials: R
authors.lastname: Schamschule
authors.forename: A B
authors.initials: AB
authors.lastname: Parusel
authors.forename: G
authors.initials: G
authors.lastname: Köhler
authors.forename: W
authors.initials: W
authors.lastname: Linert
mesh_terms: D001665:Binding Sites; D003300:Copper / Q000737:chemistry*; D004798:Enzymes / Q000737:chemistry*; D008024:Ligands; D008667:Metalloproteins / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D017550:Spectroscopy, Fourier Transform Infrared / Q000379:methods
chemical_list: D004798:Enzymes; D008024:Ligands; D008667:Metalloproteins; D009942:Organometallic Compounds; C042450:copper tetrabenzo(b,f,j,n)-1,5,9,13-tetraazacyclohexadecine; D003300:Copper