title: Synthesis, characterization and catalytic activity of copper(II) complexes containing a redox-active benzoxazole iminosemiquinone ligand.
abstract: A tridentate benzoxazole-containing aminophenol ligand HL(BAP) was synthesized and complexed with Cu(II). The resulting Cu(II) complexes were characterized by X-ray, IR, UV-vis-NIR spectroscopies, and magnetic susceptibility studies, demonstrating that the ligand is oxidized to the o-iminosemiquinone form [L(BIS)](-) in the isolated complexes. L(BIS)Cu(II)Cl exhibits a distorted tetrahedral geometry, while L(BIS)Cu(II)OAc is square pyramidal. In both solid state structures the ligand is coordinated to Cu(II)via the benzoxazole, as well as the nitrogen and oxygen atoms from the o-iminosemiquinone moiety. The chloride, or acetate group occupies the fourth and/or fifth positions in L(BIS)Cu(II)Cl and L(BIS)Cu(II)OAc, respectively. Magnetic susceptibility measurements indicate that both complexes are diamagnetic due to antiferromagnetic coupling between the d(9) Cu(II) centre and iminosemiquinone ligand radical. Electrochemical studies of the complexes demonstrate both a quasi-reversible reduction and oxidation process for the Cu complexes. While L(BIS)Cu(II)X (X = Cl) is EPR-silent, chemical oxidation affords a species with an EPR signal consistent with ligand oxidation to form a d(9) Cu(II) iminoquinone species. In addition, chemical reduction results in a Cu(II) centre most likely bound to an amidophenoxide. Mild and efficient oxidation of alcohol substrates to the corresponding aldehydes was achieved with molecular oxygen as the oxidant and L(BIS)Cu(II)X-Cs2CO3 as the catalyst.
authors.affiliation: Institute for Advanced Studies in Basic Sciences, 45137-66731 Zanjan, Iran.
authors.forename: S Esmael
authors.initials: SE
authors.lastname: Balaghi
authors.forename: Elham
authors.initials: E
authors.lastname: Safaei
authors.forename: Linus
authors.initials: L
authors.lastname: Chiang
authors.forename: Edwin W Y
authors.initials: EW
authors.lastname: Wong
authors.forename: Didier
authors.initials: D
authors.lastname: Savard
authors.forename: Ryan M
authors.initials: RM
authors.lastname: Clarke
authors.forename: Tim
authors.initials: T
authors.lastname: Storr
mesh_terms: D000627:Aminophenols / Q000737:chemistry; D001583:Benzoxazoles / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000138:chemical synthesis* / Q000737:chemistry; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D008024:Ligands; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D011789:Quantum Theory
chemical_list: D000627:Aminophenols; D001583:Benzoxazoles; D056831:Coordination Complexes; D008024:Ligands; D003300:Copper