Abstract

Synthetic procedures are described that allow access to complexes containing the cation [Cu 2(μ-OH)(μ-X)(μ-O 2CMe)(bpy) 2] + (X = Cl, Br). Reaction mixtures consisting of CuX 2, bpy, OH −, MeCO 2 − and ClO 4 − (X = Cl −) in MeOH/H 2O give blue solutions from which the products [Cu 2(OH)Cl(O 2CMe)(bpy) 2](ClO 4) · H 2O ( 1) and [Cu 2(OH)Br(O 2CMe)(bpy) 2]Br · H 2O ( 4) can be obtained in good yield. Complex 1 may also be prepared from the known complexes [Cu 2(OH)(H 2O)(O 2CMe)(bpy) 2](ClO 4) 2 ( 2) and Cu 2(OH) 2(bpy) 2 (ClO 4) 2 ( 3). Complex 1 crystallizes in monoclinic space group P2 1/ n with (at − 175°C) a = 8.434(1), b = 16.074(2), c = 9.430(1) Å, β = 98.09(1)°, Z = 2 and V = 1265.83 Å 3. The structure was solved by direct methods (MULTAN) and refined to values of conventional indices R( R w) of 3.38 (3.54)% using 1499 unique reflections with F > 2.33σ( F). The structure of the cation consists of a triply-bridged pair of five-coordinate copper(II) atoms. One of the bridging ligands is a syn, syn η 1: η 1: μ 2 acetate group, the others being the Cl − and OH − ions; a terminal bpy molecule completes five-coordination at each metal. The Cu…Cu separation is 2.957(1) Å. The metal coordination geometry is best described as distorted square-pyramidal with the Cl − ligand occupying the apical site for each metal. The oxygen atom of the water molecule is hydrogen-bonded to the OH − hydrogen. Recrystallization of 1 from warm water yields 3 in 20% yield; addition of NaClO 4 to the solution increases the yield to 40%. Complex 1 in warm water containing one equiv. of NaClO 4 and one equiv. of NaOH also gives 3 (yield 73%). The thermal decomposition, room temperature μ eff values, and electronic and IR spectra of 1 and 4 are discussed interms of the nature of bonding and structure of 1.

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