Copper(II) complexes of symmetrical and unsymmetrical tetradentate Schiff base ligands incorporating 1-benzoylacetone: Synthesis, crystal structures and electrochemical behavior

Three new copper(II) complexes [CuL1]2(ClO4)2 (1), [CuL2]ClO4 (2) and [CuL3] (3) with three Schiff base ligands [HL1 = 1-phenyl-3-{3-[(pyridin-2-ylmethylene)-amino]-propylimino}-butan-1-one, HL2 = 1-phenyl-3-[3-(1-pyridin-2-yl-ethylideneamino)-propylimino]-butan-1-one and H2L3 = 3-[3-(1-methyl-3-oxo-3-phenyl-propylideneamino)-propylimino]-1-phenyl-butan-1-one] have been synthesized and structurally characterized by X-ray crystallography. The mono-negative tetradentate asymmetric Schiff base ligands (L1)− and (L2)− are chelated in complexes 1 and 2 to form square planar copper(II) complexes. In complex 1, the two units are associated weakly through ketonic oxygen of benzoylacetone fragment to form the dimeric entity. The square planar geometry of complex 3 is unusually distorted towards tetrahedral one. All three complexes exhibit reversible cyclic voltammetric responses in acetonitrile solution corresponding to the CuII/CuI redox process. The E1/2 (−0.47 V versus SCE) of 3 shows significant anodic shift due to the tetrahedral distortion around Cu(II) compare to that of 1 and 2 (−0.82 and −0.87 V versus SCE, respectively).

Three new copper(II) complexes [CuL1]2(ClO4)2 (1), [CuL2]ClO4 (2) and [CuL3] (3) where HL1 and HL2 are two tetradentate unsymmetric Schiff base formed by condensation of 1,3-diaminopropane with benzoylacetone and pyridine-2-carboaldehyde or 2-acetylpyridine and H2L3 the symmetrical di-Schiff base of 1,3-diaminopropane and benzoylacetone have been synthesized and structurally characterized. In complex 1, the two units are associated weakly through ketonic oxygen of benzoylacetone part to form the dimeric entity. The square planar geometry of complex 3 is unusually distorted towards tetrahedral one. The E1/2 of 3 shows significant anodic shift due to the tetrahedral distortion around Cu(II).Figure optionsDownload as PowerPoint slide