title: Synthesis, characterization and dioxygen reactivity of copper(I) complexes with glycoligands.
abstract: A new family of copper(I) complexes with "glycoligands" containing a central saccharide scaffold, with 2-picolyl ether groups or 2-picolylamine or N-imidazolylamine groups, has been prepared and characterized. For this purpose, the following tetradentate ligands have been synthesized: methyl 2,3-di-O-(2-picolyl)-alpha-D-lyxofuranoside (L1), 1,5-anhydro-2-deoxy-3,4-di-O-(2-picolyl)-d-galactitol (L2), 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(2-picolyl)-alpha-D-xylofuranose (L3), and 5-(amino-N-(2-salicyl))-5-deoxy-1,2-O-isopropylidene-3-O-(methylimidazol-2-yl)-alpha-D-xylofuranose (L4). The ligands and the complexes were characterized by elemental analysis, IR, 1H and 13C NMR spectroscopies, ESI mass spectrometry, and cyclic voltammetry. Collaterally with the experimental work, HF-DFT(B3LYP/6-31G*) computations were performed to obtain additional structural information. The Cu(I) complexes are found to be pentacoordinated. The redox properties and the O2-reactivity of the Cu(I)Ln complexes have been studied. Reactions of Cu(I) complexes with dioxygen in ethanol yield stable Cu(II) complexes as confirmed by UV-visible spectrophotometry and EPR spectroscopy.
authors.affiliation: Institut de Chimie Moléculaire de Reims, Equipe Chimie de Coordination, Université de Reims Champagne-Ardenne, UMR CNRS 6229, Faculté des Sciences, BP 1039, F-51687, Reims cedex 2, France.
authors.forename: Ziad
authors.initials: Z
authors.lastname: Damaj
authors.forename: Federico
authors.initials: F
authors.lastname: Cisnetti
authors.forename: Laurent
authors.initials: L
authors.lastname: Dupont
authors.forename: Eric
authors.initials: E
authors.lastname: Henon
authors.forename: Clotilde
authors.initials: C
authors.lastname: Policar
authors.forename: Emmanuel
authors.initials: E
authors.lastname: Guillon
mesh_terms: D003300:Copper / Q000737:chemistry* / Q000378:metabolism; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D006001:Glycoconjugates / Q000378:metabolism*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry* / Q000378:metabolism; D021241:Spectrometry, Mass, Electrospray Ionization; D013056:Spectrophotometry, Ultraviolet
chemical_list: D006001:Glycoconjugates; D009942:Organometallic Compounds; D003300:Copper; D010100:Oxygen