Inhaltszusammenfassung

The reaction of the bidendate 1-azadiene ligands Me2N-(CH2)(n)-N=CH-CH=CH-Ph with CuX results in the formation of the dimeric compounds [ACuX](2) and [BCuX](2) (A: n = 2, B: n = 3, X: I, Cl). The structure of complex 1 [ACuI](2) was determined by X-ray crystal structure analysis. 1 consists of two tetrahedrally coordinated Cu atoms connected by two iodo bridges. (Cu-Cu bond length: 261 pm). The ligand Me-N(CH2CH2N=CH-CH=CH-Ph)(2) (C) reacts with CuX to form the monomeric complexes [CCuX] (5: ...The reaction of the bidendate 1-azadiene ligands Me2N-(CH2)(n)-N=CH-CH=CH-Ph with CuX results in the formation of the dimeric compounds [ACuX](2) and [BCuX](2) (A: n = 2, B: n = 3, X: I, Cl). The structure of complex 1 [ACuI](2) was determined by X-ray crystal structure analysis. 1 consists of two tetrahedrally coordinated Cu atoms connected by two iodo bridges. (Cu-Cu bond length: 261 pm). The ligand Me-N(CH2CH2N=CH-CH=CH-Ph)(2) (C) reacts with CuX to form the monomeric complexes [CCuX] (5: X = I, 6: X = Cl). The crystal structure of 5 shows that the ligand acts as a tridendate ligand. The bond lengths of the CuN(sp(2)) bonds are significantly shorter than the Cu-N(sp(3)) distance. Reacting the podand-type ligands N(CH2CH2-N=CH-R)(3) (D: R = Ph, E: R = -CH=CH-Ph) with CuX yields the ionic complexes 7 [DCu][CuCl2] and 8 [ECu][CuCl2]. 7 was characterized by X-ray analysis which confirmed that D acts as a four-dendate podand ligand. The compounds 1-8 are unreactive towards CO2 but take up O-2 even at deep temperatures. At -78 degrees C the orange-red complex 4 [BCuCl](2) reacts with O-2 in CH2Cl2 to form a deep violet solution, but the primary product of the oxidation could not be isolated. It reacts at room temperature to form the green complex 9 [mu-Cl, mu-OH][BCuCl](2). The X-ray structure analysis of 9 confirms that a dimeric Cu-II complex is formed in which both a chloro- and a hydroxo group are bridging the monomeric units. The Cu-II centers exhibit a distorted tetragonal-pyramidal coordination. The pathway of the reaction with O-2 will be discussed. » weiterlesen» einklappen

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