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Synthesis, spectroscopic and structural characterization of some novel adducts of copper(II) salts with unidentate nitrogen bases

Syntheses, spectroscopic characterization and single crystal X-ray studies are reported for a number of complexes of copper(II) salts with simple monodentate nitrogen bases. The 1:4 adduct of copper(II) sulfate with 3,5-dimethylpyridine (m2py) CuSO4¡¤4m2py, takes the form [(O3SO)Cu(m2py)4], the Cu-O vector of the square-pyramidal coordination environment being disposed on the 4-axis in tetragonal space group P4/n. The complex CuCO3¡¤ Cu(NCS)2¡¤4py is a linear polymer, taking the form ?O¡¤Cu(py)2¡¤O¡¤C{O¡¤Cu(py) 2(NCS)2}¡¤O¡¤Cu(py)2? (etc.), all atoms lying in the mirror plane of space group Pnma, excepting the pair of ‘py’ (pyridine) ligands disposed to either side. In Cu(OH)I¡¤3/ 4I2¡¤2py¡¤1/2MeCN ? [{(py)2Cu(OH)} 4](I3)3I¡¤2MeCN a novel cubanoid tetranuclear cation is found (2-symmetry). The EPR spectra of the above compounds show a trend in the anisotropy of the g-values that correlates well with the crystal structures. Obtained only in small quantities but supported by single crystal X-ray studies are the adduct of Cu(OH)Cl with pyrrolidine (pyrr), Cu(OH)Cl:pyrr (1:3), which takes the centrosymmetric binuclear form [(pyrr)3Cu(mu-OH)2Cu(pyrr)3]Cl2, the copper atom being disposed in a distorted trigonal bipyramidal array, and the adduct 3CuCl2¡¤CuO¡¤4quin, [Cu4Cl 6O(quin)4]Cl2, which contains the familiar Cu4Cl6O core with monodentate quinuclidine (quin) attached to the copper atoms; this compound crystallizes in the cubic space group 4?3m.

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Reference£º
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”