Martin, Eddy, Spendley, Claire, Mountford, Andrew J., Coles, Simon J., Horton, Peter N., Hughes, David L., Hursthouse, Michael B. and Lancaster, Simon J. (2008) Synthesis, structure, and supramolecular architecture of benzonitrile and pyridine adducts of bis(pentafluorophenyl)zinc: pentafluorophenyl-aryl interactions versus homoaromatic pairing. Organometallics, 27 (7), 1436-1446. (doi:10.1021/om701127p).
Abstract
Treatment of (C6F5)2Zn(toluene) with 2 equiv of a series of benzonitrile or pyridine derivatives yielded the complexes (C6F5)2Zn(L)2 (where L = benzonitrile, 4-(phenyl)benzonitrile, 4-(N-pyrrolyl)benzonitrile, pyridine, 4-(phenyl)pyridine, and 4-(N-pyrrolyl)pyridine). The four-coordinate solution-phase nature of these complexes was confirmed by a series of variable-temperature 19F NMR experiments and comparison to (C6F5)2Zn(2,2?-bipy). The solvent-free solid-state structures of each of the four-coordinate adducts and the toluene solvate of (C6F5)2Zn(NCC6H4C6H5)2 were determined by single-crystal X-ray diffraction and have distorted tetrahedral geometries. Analysis of the crystal packing revealed a preponderance of offset face-to-face homo?aryl and embrace-like interactions over the hetero?aryl, pentafluorophenyl?phenyl, interaction. These aryl?aryl synthons serve to assemble paired, one- and three-dimensional supramolecular architectures.
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