10.1002/chem.201706061
Chemistry - A European Journal
FULL PAPER
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Kinetic experiments: For a stock solution, 1a (0.72 g, 5.1 mmol), diglyme
(72 µl, 0.5 mmol) and toluene (6 ml) were mixed in the glove box. For each
sample, 500 µl stock solution was filled in a J. Young NMR tube containing
a glass capillary tube filled with acetone-d6. The solution was degassed
and 2 (63 mg, 0.42 mmol) was added by vacuum transfer. To determine
ΔG/ΔH/ΔS, the reaction progress was monitored by 19F NMR
spectroscopy at -30, -15, 0 °C, respectively. The conversion of the
substrate was determined from 19F NMR spectra by integration of product
and starting material resonances (detailed data is given in the Supporting
Information).
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Calculations. All structures were fully optimized at the M06-2X(PCM)[38]
/6-31+(2d,p) level using Gaussian09[39] coupled to an external optimizer
(PQS, OPTIMZE routine)[40] within the BOPT software package.[41] An
ultrafine grid (Int(Grid=ultrafine)) and standard SCF convergence quality
settings (Scf=tight) for Gaussian single point calculations were used. The
nature of each stationary point was checked with an analytical second-
derivative calculation (no imaginary frequency for minima, exactly one
imaginary frequency for transition states, corresponding to the reaction
coordinate) and the accuracy of the TS was confirmed with an IRC scan
Solvent influence (toluene, ε=2.3741) was modelled explicitly, using the
polarizable continuum model (PCM) implemented in the Gaussian 09
software suite. The M06-2X functional has been shown to yield accurate
results for systems involving aluminium systems.[42]
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The authors would like to thank Prof. P. H. M. Budzelaar
(University of Naples, Federico II., Italy and U-Manitoba,
Winnipeg) for generous donation of CPU time. Support from the
Deutsche Forschungsgemeinschaft (DFG) and the GRK 1582
(Fluorine as a Key Element) is gratefully acknowledged.
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Keywords: homogeneous catalysis • DFT • organocatalyst •
aluminium hydrides • hydrodefluorination
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