Catalysis Science & Technology
Paper
II GC equipped with a flame ionization detector (FID) detector
and a Agilent HP-1 methyl siloxane column. Retention times
were confirmed by comparison with authentic materials. Peak
areas were referenced against HMB (hexamethylbenzene) as
internal standard, interpolating from calibration curves span-
ning the experimental concentration regime. Agreement be-
tween replicate runs was within 5%.
magnetic stir bar, and bubbling was observed upon mixing.
The reaction was allowed to stir under N2 overnight (ca. 18
h), resulting in a black solution. Volatiles were then removed
under vauum, and the resulting black solid was washed with
cold hexanes (3
× 15 mL) and then dried, giving
CpCoIJI)2IJPPh2Me). Yield: 466 mg (81%). 1H NMR (C6D6, 300
MHz) δ 7.71 (m, 4H), 7.05 (m, 6H), 4.51 (s, 5H, Cp), 2.29 (d,
3H, CH3). 31P{1H} NMR δ 23.7 ppm.
General procedure for the synthesis of CpRCoIJI)IJ(CF2)3CF3)IJCO)
(CpR = η5-cyclopentadienyl or η5-pentamethylcyclopentadienyl)
General procedure for catalytic fluorination of acyl chlorides
A glass vial was charged with a magnetic stir bar, AgF (55 mg,
0.434 mmol), CpCoIJI)2IJPPh2Me) (5 mg, 0.0086 mmol), and
CH2Cl2 (1.0 mL). The vial was capped and covered with
aluminum foil, and stirred for 5 minutes. A solution of acyl
chloride 1 (0.173 mmol) in CH2Cl2 (1.0 mL) was added, and
the resulting mixture was again covered with aluminum foil
Caution: this experiment produces CO gas. A solution of
ICF2CF2CF2CF3 (2.89 g, 11.65 mmol) in toluene (5 mL) was
added to
a 100 mL bomb containing a solution of
CpRCoIJCO)2 (2.87 mmol) (5 mL) and stirred under N2 (with
allowance for pressure release caused by CO generation), at
room temperature for 48 hours. Over the course of the reac-
tion, the color changed from dark red to green-brown. The
solvent/volatiles were removed under vacuum, affording a
dark green-brown solid, which was purified by washing with
hexane (3 × 15 mL), followed by recrystallization from a
concentrated CH2Cl2 solution and further washing with cold
hexane.
and stirred for
4 or 4.5 hours. A solution of 1,3-
bisIJtrifluoromethyl)benzene (0.026 mmol) in CDCl3 (0.5 mL)
was then added to the mixture, and an aliquot was then ana-
lyzed using 19F NMR to determine the yield of 2.
General procedure for the synthesis of acyl fluorides 2b, 2k
A glass vial was charged with a magnetic stir bar, AgF (205
mg, 1.62 mmol), CpCoIJI)2IJPPh2Me) (16 mg, 0.028 mmol), and
CH2Cl2 (2.0 mL). The vial was capped and covered with alu-
minum foil, and stirred for 5 minutes. A solution of acyl chlo-
ride 1b/k (0.54 mmol) in CH2Cl2 (2.0 mL) was added, and the
resulting mixture was again covered with aluminum foil and
stirred for 4 hours. The mixture was then filtered through a
small plug of silica gel, and eltued with CH2Cl2 (5 mL). The
filtrate was then evaporated to dryness, and the resulting resi-
due was triturated with Et2O (2 mL), and dried under vacuum
to give 2b/k. The NMR data for 2b and 2k are consistent with
that previously reported.8,26,27
CpCoIJI)IJ(CF2)3CF3)IJCO) (M3)
1
Yield: 550 mg (40%). H NMR (C6D6, 300 MHz) δ 4.46 (s, 5H).
19F NMR (C6D6, 282 MHz) δ −55.2 (dd, JFF = 16 Hz, JFF = 13
2
3
Hz, 2F, −CF2CF2CF2CF3, FA/B), −81.6 (m, 3F, −CF2CF2CF2CF3),
2
−108.9 (d, JFF = 280 Hz, 1F, −CF2CF2CF2CF3, FA/B), −112.5 (d,
2JFF = 280 Hz, 1F, −CF2CF2CF2CF3, FA/B), −124.3 (d, JFF = 258
2
2
Hz, 1F, −CF2CF2CF2CF3, FA/B), −126.6 (d, JFF = 258 Hz, 1F,
−CF2CF2CF2CF3, FA/B). 13C{1H} NMR (C6D6, 75 MHz) δ 199.6
(s), 120.5 (m), 116.7 (m), 113.0 (m), 110.2 (m), 90.2 (s). IR
(nujol) 2059, 2080 cm−1. Anal. calcd for C10H5CoF9IO: C,
24.12; H, 1.01%. Found: C, 23.57, H: 0.883%.
4-Nitrobenzoyl fluoride (2b)
Cp*CoIJI)IJ(CF2)3CF3)IJCO) (M5)
Yield: 68 mg (75%). 1H NMR (CDCl3, 300 MHz) δ 8.39 (d,
Yield: 526 mg (50%). 1H NMR (C6D6, 300 MHz) δ 1.41 (s,
3
2
3JHH = 8.5 Hz, 2H, o-Ar-H), 8.25 (d, JHH = 8.5 Hz, 2H, m-Ar-
15H, CH3). 19F NMR (C6D6, 282 MHz) δ −68.2 (d, JFF = 261
2
H). 19F NMR (CDCl3, 282 MHz) δ 20.6 (s).
Hz, 1F, −CF2CF2CF2CF3, FA/B) −70.8 (d, JFF = 261 Hz, 1F,
−CF2CF2CF2CF3, FA/B), −81.5 (s, 3F, −CF2CF2CF2CF3), −106.9
2
2
3,4,5-trisIJMethoxy)benzoyl fluoride (2k)
(d, JFF = 288 Hz, 1F, −CF2CF2CF2CF3, FA/B), −110.0 (d, JFF
=
2
1
288 Hz, 1F, −CF2CF2CF2CF3, FA/B), −124.8 (dt, JFF = 289 Hz,
Yield: 67 mg (58%). H NMR (CDCl3, 300 MHz) δ 7.27 (s, 2H,
3JFF = 15 Hz, 1F, −CF2CF2CF2CF3, FA/B), −126.0 (dt, JFF = 289
2
o-Ar-H), 3.95 (s, 3H, p-OMe), 3.91 (s, 6H, m-OMe). 19F NMR
(CDCl3, 282 MHz) δ 15.9 (s).
3
Hz, JFF = 15 Hz, 1F, −CF2CF2CF2CF3, FA/B). 13C{1H} NMR
(C6D6, 75 MHz) δ 203.3 (s) 120.6 (m), 116.7 (m), 113.2 (m),
110.3 (m), 106.7 (m), 103.4 (s), 10.3 (s). IR (nujol) frequency:
2006, 2051 cm−1. Anal. calcd. for C15H15CoF9IO: C, 31.71; H,
2.66%. Found: C, 31.91; H, 2.58%.
Conflicts of interest
There are no conflicts of interest to declare.
Acknowledgements
Synthesis of CpCoIJI)2IJPPh2Me)
Caution: this experiment produces CO gas. A solution of PPh2-
Me (197 mg, 1.02 mmol) in toluene (5 mL) was slowly added
via cannula transfer to a 100 mL bomb containing a solution
of CpCoIJI)2IJCO) (400 mg, 0.99 mmol) in toluene (5 mL) and a
We thank the NSERC and the Canada Research Chairs pro-
gram for generous financial support and the University of
Ottawa, Canada Foundation for Innovation, and Ontario Min-
istry of Economic Development and Innovation for essential
This journal is © The Royal Society of Chemistry 2017
Catal. Sci. Technol.