Lewis-base adducts of group 11 metal(I) compounds. XXXI. Reaction of 2,6-bis[1-phenyl-1-(pyridin-2-yl)ethyl]pyridine (L), and copper(I) halides in acetonitrile: Structural characterization of salts of the [(MeCN)Cu (meso-L)]+ cation
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Reaction of 2,6-bis[l-phenyl-1-(pyridin-2-yl)ethyl]pyridine, L, with copper(1) chloride, bromide, and iodide in acetonitrile solution has been shown to yield salts, structurally characterized by single-crystal X-ray diffraction methods as [( MeCN ) CuL ]+ [ ClCuCl ]-, (1), [( MeCN ) CuL ]+2 [XCuX2CuX]2-, X = Br (2), I (3) (both isomorphous ), all as yellow needles, and a form of (3), orange blocks, as the hemiacetonitrile solvate, (4), [( MeCN ) CuL ]+2 [IcuI2Cul]2-. MeCN . The same cation is common to all four species, containing four-coordinate copper(r), with L as meso -tridentate ligand; in (4), the most precisely defined example, Cu-N( MeCN ) is 1.919(5) Ŭ the shortest copper(1) acetonitrile distance known, while Cu-N(L) are 2.065(5)-2.073(5) Ů The reason for non-formation of species of the type [ LCuX ] appears to lie in the tridentate ligand conformation which permits coordination of acetonitrile but not larger halide species.
Australian Journal of Chemistry