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Abstract
The coordination behavior of pyridine carbinoxide [NC5H4(CH2O)-2 or OPy] with copper in organic solvents was crystallographically determined. Initial attempts to generate the Cu(II) OPy derivatives from an alcoholysis exchange of Cu(OCH3)2, with H–OPy in toluene, led to the isolation of [Cu(µc-OPy)(OcPy)]2 (1, “c” indicates chelation). The square-based pyramidal geometries noted for each Cu center resulted from one OcPy and two µc-OPy ligands, generating an unusual Ci symmetry. From the reaction of H–OPy and the Cu(I) species Cu(C6H2(CH3)3-2,4,6), mononuclear Cu(II) complex Cu(OcPy)2(H–OPy)2 (2) was isolated. Compound 2 is unusual in that it adopts a square planar arrangement around the Cu metal center using two OcPy ligands; however, the metal center also coordinates with two H–OPy molecules forming an octahedral geometry. Upon dissolution in water, both 1 and 2 react to form the previously reported Cu(OcPy)2 · 2H2O (3). Attempts to add a Lewis base through dissolution of 1 in selected solvents (i.e., tetrahydrofuran, pyridine, 1-methylimidazole) led to [Cu(µc-OPy)(OcPy)]2 · H2O (4), which possesses a C 2 symmetry. The water was believed to be extracted from the “dry” solvents. A Cl derivative was also solved for the Cu(II)/Cu(I) species [Cu(OPy)2]2[CuCl(H–OPy)2]2 (5) from tetrahydrofuran dried over apparently contaminated sieves.
Acknowledgments
The authors thank Sandia, a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the United States Department of Energy under contract DE-AC04-94AL85000.