Compound E1

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Compound data: Crystallographic data

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

In a glovebox, palladium complex (C2) (0.02 mmol, 15.4 mg, 1 equiv), KOAc (0.1 mmol, 10 mg, 10.0 equiv), and anhydrous THF (0.8 mL) were added to a J-Young NMR tube. After the resulting mixture was shaken for 1 min, TMSCF₂Br (0.1 mmol, 15.6 μL, 2.0 equiv) was added. The NMR tube was screw capped and shaken for 10 min. The reaction mixture was diluted with 10 mL pentane and purified by a short silica gel column (acetone : pentane = 1 : 2) to give pure complex E1 (7.4 mg, 45% yield; 65% yield, determined by ¹⁹F NMR) as a pale yellow solid (NOTE: the low isolated yield of E1 is because of the relatively strong adsorption of complex E1 by silica gel in the column). ¹H NMR (400 MHz, CD₂Cl₂) δ 7.75 – 7.62 (m, 8 H), 7.42 (t, J = 7.2 Hz, 4 H), 7.38 – 7.30 (m, 10 H), 7.21 (t, J = 7.7 Hz, 2 H), 7.06 – 6.94 (m, 2 H), 5.13 (tt, J = 54.8 Hz, 6.7 Hz, 1 H), 1.79 (s, 6 H). ¹³C NMR (101 MHz, CD₂Cl₂) δ 155.08 (d, J = 5.0 Hz), 155.04 (d, J = 5.0 Hz), 134.98 -134.84 (m), 131.65, 131.39 (d, J = 22.2 Hz), 131.17 (d, J = 22.2 Hz), 130.90, 128.81 (d, J = 5.3 Hz), 128.75 (d, J = 5.3 Hz), 127.98, 124.82 (d, J = 4.0 Hz), 124.78 (d, J = 4.0 Hz), 122.60 (d, J = 23.3 Hz), 122.36 (d, J = 23.3 Hz), 111.84 (t, J = 249.8 Hz), 36.58, 28.68. (NOTE: The signal for carbon corresponding to Pd-CF₂CF₂H is not shown in the spectrum). ¹⁹F NMR (376 MHz, CD₂Cl₂) δ -79.0 – -83.0 (m, 2 F), -130.8 (d, J = 54.8 Hz, 2 F). ³¹P NMR (162 MHz, CD₂Cl₂) δ 14.06 (t, J = 46.2 Hz, 2 P). Sample for the X-ray crystal structure analysis was recrystallized from CHCl₃/Hexane.