Pyridine and benzonitrile adducts of bis(4-nonafluorobiphenyl)zinc

Treatment of (ArF′)2Zn(OEt2)2 (ArF′ = 4-C6F5C6F4) with 2 equiv. of benzonitrile, 4-(phenyl)benzonitrile, 4-(pyrrolyl)benzonitrile, pyridine, 4-(phenyl)pyridine or 4-(pyrrolyl)pyridine in dichloromethane afforded the corresponding adducts (ArF′)2ZnL2 in near quantitative yield. The 2,2′-bipyridine adduct was prepared similarly. Multinuclear NMR spectroscopy indicated that zinc′s four-coordinate character was maintained in solution. The pyridine complex crystallized from dichloromethane with a solid-state structure free of face-to-face aryl–aryl interactions. In contrast, the 4-(pyrrolyl)pyridine adduct crystallized from both dichloromethane and 1,2-difluorobenzene, with solvent of crystallization, but otherwise essentially identical supramolecular architectures assembled through aryl–aryl synthons, including a face-to-face pentafluorophenyl–pyrrole interaction.

Graphical abstractTreatment of (ArF′)2Zn(OEt2)2 (ArF′ = 4-C6F5C6F4) with 2 equiv. of 4-(pyrrolyl)pyridine in dichloromethane afforded the corresponding adduct in near quantitative yield. (ArF′)2Zn(NC5H4NC4H4)2 crystallized from both dichloromethane and 1,2-difluorobenzene, with solvent of crystallization, but otherwise essentially identical supramolecular architectures assembled through aryl–aryl synthons, including a face-to-face pentafluorophenyl–pyrrole interaction.Figure optionsDownload full-size imageDownload as PowerPoint slide