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One-Pot Route to X‑perfluoroarenes (X = Br, I) Based on FeIII-Assisted C–F Functionalization and Utilization of These Arenes as Building Blocks for Crystal Engineering Involving Halogen Bonding
journal contribution
posted on 2020-07-01, 15:18 authored by Anton
V. Rozhkov, Anastasiya A. Eliseeva, Sergey V. Baykov, Bartomeu Galmés, Antonio Frontera, Vadim Yu. KukushkinPerfluorinated
arenes (benzeneF derivatives, diphenylF, naphthaleneF) were converted into X-perfluoroarenes
(X = Br, I) via the developed one-pot protocol based on [Fe(acetylacetonate)3]-assisted C–F functionalization. The syntheses proceed
under mild conditions and employ readily available perfluorinated
arenes, which are treated with EtMgBr followed by addition of X2/[Fe(acetylacetonate)3] (0.8 mol %); yields range
from good to moderate. The σ-hole donor properties of the obtained
mono- and di-X-perfluoroarenes and the significance of these species
for halogen-bonding-based crystal engineering was illustrated in a
series of postsynthetic experiments, all supported by density functional
theory (DFT) energy calculations, molecular electrostatic potential
(MEP) surface analysis, and the quantum theory of atoms in molecules
(QTAIM). These include (i) a solid-state X-ray diffraction study of
X-perfluoroarene self-association (dimerization) via iodine σ-holeelectron
belt interactions (three X-ray structures) and (ii) verification of
X-perfluoroarene σ-hole donor abilities by their interactions
with iodides acting as external σ-hole acceptors (five X-ray
structures); a Hirshfeld surface analysis was performed for all eight
structures.
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X-perfluoroarene self-associationhalogen-bonding-based crystal engin...BrX-ray structuresFe IIICrystal Engineeringperfluorinated arenesbenzene F derivativesone-pot protocolnaphthalene FHirshfeld surface analysisquantum theoryinteractionBuilding BlocksX-ray diffraction studyσ- hole acceptorsHalogen Bonding Perfluorinated arenesDFTX-perfluoroarene σ- hole donor abil...MEPpostsynthetic experimentsdiphenyl FOne-Pot Routeσ- hole donor propertiessurface analysisenergy calculationsQTAIM
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