Currently, the chemistry of organofluorine compounds is a leading and rapidly developing area of organic chemistry. Fluorine present in a molecule largely determines its specific chemical and biological properties. This thematic issue covers the trends of organofluorine chemistry that have been actively developed in Russia the last 15 – 20 years. The review describes nucleophilic substitution and heterocyclization reactions involving fluorinated arenes and quinones and skeletal cationoid rearrangements in the polyfluoroarene series. The transformations involving CF3-substituted carbocations and radical cations are considered. Heterocyclization and oxidative addition reactions of trifluoroacetamide derivatives and transformations of the organic moiety in polyfluorinated organoboranes and borates with retention of the carbon – boron bond are discussed. Particular attention is devoted to catalytic olefination using freons as an efficient synthetic route to fluorinated compounds. The application of unsymmetrical fluorine-containing N-heterocyclic carbene ligands as catalysts for olefin metathesis is demonstrated. A variety of classes of organofluorine compounds are considered, in particular, polyfluorinated arenes and 1,2-diaminobenzenes, 1-halo-2-trifluoroacetylacetylenes, α-fluoronitro compounds, fluorinated heterocycles, 2-hydrazinylidene-1,3-dicarbonyl derivatives, imines and silanes. The potential practical applications of organofluorine compounds in fundamental organic chemistry, materials science and biomedicine are outlined.
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In contrast to aromatic carboxylates, the coordination polymers based on their perfluorinated analogues are not numerous. Here we present a series of six Zn(ii) coordination polymers of different dimensionalities (1D, 2D, and 3D) and porosities based on octafluorobiphenyl-4,4'-dicarboxylate (oFBPDC) and N-containing co-ligands (ur, dabco, and bpy). These complexes are characterized by single-crystal X-ray diffraction, PXRD, FT-IR, elemental analysis, and TGA. The metal-organic frameworks [Zn(CHCONH)(oFBPDC)] (1) and [Zn(oFBPDC)(dabco)] (4) are shown to be porous with BET surface areas of 470 m g and 441 m g, respectively. In addition, compound 4 shows selectivity factors of 11.3, 4.9 and more than 6 for the binary gas mixtures CO/N, CO/CH and benzene/cyclohexane, respectively. The measurements for pressed powders and water droplet give water contact angles of 136° for 4 and 133° for (Hbpy)[Zn(bpy)(oFBPDC)] (5). Low water uptake indicates that both 4 and 5 belong to highly hydrophobic solids.
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