A Series of Dinuclear Complexes with a Flexible Naphthalene-Spacer and MOM-Cleavage by Pre-coordinated Lewis Acids

作者：Jany Thomas; Gruschka Claudia Horstmann Nee; Boegge Hartmut; Stammler Anja; Glaser Thorsten^*

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2015, 641(12-13): 2157-2168.

DOI：10.1002/zaac.201500553

• N, O ligands
• Copper
• Iron
• UV/Vis spectroscopy
• Cyclic voltammetry

The synthesis, spectroscopic, electrochemical, magnetic, and structural characterization of the dinuclear series of complexes [( MOM2tomMe){MIICl2} 2] ( MII = ZnII, CuII, NiII, CoII, FeII) and, for comparison, the structure of the complex [( MOM2tom){ZnIICl2} 2] are presented. The metal ions are five- coordinate in N3Cl2 environments. The coordination polyhedra are evaluated in the solid- state by singlecrystal X- ray crystallography and in solution by UV/ Vis/ NIR spectroscopy for the CuII and FeII complexes. All complexes exhibit a ligand- centered irreversible oxidation in the range 1.17- 1.40 V vs. Fc+/ Fc, whereas the complexes with FeII, CoII, and NiII exhibit additional reversible metal- centered oxidations of 0.09, 0.70, and 0.87 V vs. Fc+/ Fc, respectively. The coordination of the chloride ligands saturates the Lewis- acidity of the metal ions so that the MOM groups are not cleaved. Bands at 1161 and 1020 cm- 1 in the FT- IR spectra are a signature for the presence of the MOM groups. Reaction with copper( II) acetate at room temperature results in the complex [( MOM2tomMe){CuII( OAc) 2} 2] while the reaction at 50 degrees C for several hours resulted in the simultaneous MOM cleavage and complexation and thus isolation of [( tomMe){Cu( OAc)} 2]. This successful synthetic route will be applied to establish a series of [( tomMe){M( OAc)} 2] with different metal ions in order to compare their DNA binding ability and cytotoxicity to cancer cells to that of the copper( II) complex.

• 出版日期2015-10