Wrapping an Organic Reducing Reagent in a Cationic Boron Complex and Its Use in the Synthesis of Polyhalide Monoanionic Networks
作者： Viktoriia Vitske , Hendrik Herrmann , Markus Enders , Elisabeth Kaifer , Hans-Jörg Himmel
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摘要: The reaction between BF(3)⋅OEt(2) and one of two guanidines, 1,8-bis(tetramethylguanidinyl)naphthalene (btmgn) 1,2,4,5-tetrakis(tetramethylguanidinyl)naphthalene (ttmgn), yields the salts [(btmgn)(BF(2))]BF(4) [(ttmgn)(BF(2))(2)](BF(4))(2). NMR spectroscopic data show that boron atoms in cation anion exchange case [(ttmgn)(BF(2))(2)](BF(4))(2), but not [(btmgn)(BF(2))]BF(4). rate constant for this was estimated to be 4 s(-1) at 80 °C solutions CH(3)CN. These were subsequently used reduction dihalides Br(2) or I(2) give polyhalide salts. We report synthesis first complete characterization (including structural analysis) contain pentabromide monoanions. In these salts, Br(5)(-) anions interact dimeric units polymeric chains. Our results are compared previous quantum chemical calculations on gas-phase structure anion. possible pathways lead polyhalides evaluated. is accompanied by ttmgn oxidation, whereas initiated aromatic substitution.
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