1
04
S. Yuan et al. / Inorganica Chimica Acta 439 (2016) 100–105
6.42%. IR (Nujol mull, cmꢀ1): 1877
m
(C@O), 1601
m
(C@C), 934
), 1.22 (s,
6 6
), 6.47 (s broad, Ar–H), 7.20 (s broad, Ar–H); P NMR (C D ,
q
3
. Conclusions
1
(
PMe
PMe
300 K, ppm): 18.6 (s, PCH
3
). H NMR (C
6
D
6
, 300 K, ppm): 0.87 (s, PMe
3
3
1
In conclusion, the reaction of fluoroaldehydes with CoMe
3
1
9
(
PMe
3
)
4
afforded the corresponding fluorophenyl carbonyl cobalt
3
). F NMR (C
D
6 6
, 300 K, ppm): ꢀ147.7
(
I) complexes 1–3. The reactions of complex 1 with CO and
(t, J = 19.74 Hz, 1F), ꢀ144.7 (d, J = 19.74 Hz, 1F), ꢀ83.6 (s, 1F).
pentafluorophenyl bromide provided dicarbonyl cobalt(I) complex
and cobalt(II) bromide 5 with the formation of perfluorinated
4
4.5. Synthesis of complex 4
diphenyl while the combination of complex 3 with pheny-
lacetylene delivered hydrido diethinyl cobalt(III) complex 6 with
A sample of 1 (0.46 g, 1.07 mmol) in 50 mL of pentane at room
temperature was stirred under 1 bar of CO for 12 h, and the red
solution slowly turned yellow. The reaction solution was then fil-
tered. Crystallization at ꢀ20 °C afforded light yellow crystals of 4
1
,2,4-trifluorobenzene as byproduct. The molecular structures of
1, 4 and 5 were determined by single crystal X-ray diffraction.
The catalytic decarbonylation of 2,4,5-trifluoro-benzaldehyde to
1
,2,4-trifluorobenzene by CoMe(PMe
3
)
4
was explored.
(0.21 g, 51.2%). m.p.: 110–112 °C. Anal. Calc. for C14
H21CoF
2
O
P
2 2
(
(
q
380.19 g/mol): C, 44.23; H, 5.57. Found: C, 44.38; H, 5.44%. IR
ꢀ1
Nujol mull, cm ): 1956
m(C@O), 1898
m
(C@O) 1610
m
(C@C), 947
4
. Experimental
1
0
2
4
(PMe
3
). H NMR (C
6 6
D , 300 K, ppm): 1.03 (t , | J(P,H) + J(P,H)|
=
9 Hz, 18H, PMe
3
), 6.47(m, 2H, Ar–H), 7.17 (s broad, 1H, Ar–H);
4.1. General procedures and materials
3
1
19
6 6 3 6 6
P NMR (C D , 300 K, ppm): 40.9 (s, PCH ). F NMR (C D ,
3
00 K, ppm): ꢀ120.1 (d, J = 5.64 Hz, 1F), ꢀ79.1 (d, J = 5.64 Hz, 1F).
Standard vacuum techniques were used in manipulations of
volatile and air sensitive materials. Solvents were dried by known
procedures and distilled under nitrogen before use. Literature
1
3
C NMR (C
6
D
6
, 300 K, ppm): 147.48 (d, J = 19.50 Hz), 110.40 (d,
0
J = 19.50 Hz), 101.70 (dd, J = 38.25, 22.5 Hz), 30.17(s), 18.86 (t ,
J = 33 Hz).
3 4
methods were used in the preparation of CoMe(PMe ) . [17] Infra-
ꢀ1
red spectra (4000–400 cm ), as obtained from Nujol mulls
between KBr disks, were recorded on a Bruker ALPHA FT-IR Spec-
4.6. Synthesis of complex 5
1
13
31
19
trometer. H, C, P and F NMR spectra (300, 75, 121 and
82 MHz, respectively) were recorded on a Bruker Avance 300
A sample of 1-bromo-2,3,4,5,6-pentafluoro-benzene (0.30 g,
2
1
3
31
1.21 mmol) in 20 mL of pentane was slowly combined with a
solution of 1 (0.52 g, 1.21 mmol) in 20 mL pentane at ꢀ80 °C. This
mixture was allowed to warm to 20 °C and stirred for 48 h to form
a brown solution. The reaction solution was then filtered. Crystal-
lization at ꢀ20 °C afforded brown crystals of 5 (0.26 g, 44.6%). m.p.:
spectrometer. C and P NMR resonances were obtained with
broadband proton decoupling. Elemental analyses were carried
out on an Elementar Vario EL III. Melting points were measured
in capillaries sealed under N
2
and were uncorrected.
1
3
1
20–122 °C. Anal. Calc. for C15
7.52; H, 6.30. Found: C, 37.67; H, 6.15%. IR (Nujol mull, cm ):
H
30BrCoF
2
P
3
(480.15 g/mol): C,
4
.2. Synthesis of complex 1
ꢀ1
1
576
m
(C@C), 944
q(PMe
3
). The signals of H NMR (C
, 300 K, ppm) were strongly broadened.
, 300 K, ppm): ꢀ77.8 (s, 1F), ꢀ121.8 (d, J = 5.64 Hz,
F) ppm. The yield of perfluorobiphenyl was 67.2% determined
6 6
D , 300 K,
2
,4-Difluoro-benzaldehyde (0.36 g, 2.53 mmol) was added drop-
31
6 6
ppm) and P NMR (C D
wise to a solution of CoMe(PMe (0.96 g, 2.53 mmol) in 30 mL of
3
)
4
19
6 6
F NMR (C D
pentane at ꢀ80 °C. This mixture was allowed to warm to ambient
temperature to form a red mixture with powders, the powders
were dissolved when stirred for 6 h sequentially. The dark red reac-
tion solution was then filtered. Complex 1 (0.93 g, 2.17 mmol) was
isolated as red crystals in 86% yield from pentane at 20 °C. m.p.:
1
19
by F NMR spectroscopy with trifluoromethyltoluene as the exter-
nal standard.
4.7. The reaction of complex 3 with phenylethyne
1
4
1
05–107 °C. Anal. Calc. for
4.87; H, 7.06. Found: C, 45.03; H, 7.01%. IR (Nujol mull, cm ):
16 2 3
C H30CoF OP (428.26 g/mol): C,
ꢀ1
A sample of phenylethyne (0.21 g, 2.06 mmol) in 20 mL of pen-
1
880
m(C@O), 1572
m
(C@C), 940
3 6 6
q(PMe ). H NMR (C D , 300 K,
tane was slowly combined with a solution of complex 3 (0.46 g,
ppm): 0.92 (s, 27H, PMe
3
), 6.56 (s broad, 2H, Ar–H), 7.19 (s broad,
1
.03 mmol) in 20 mL of pentane at ꢀ80 °C. This mixture was
3
1
19
1
(
6 6 3
H, Ar–H); P NMR (C D , 300 K, ppm): 19.0 (s, PCH ). F NMR
allowed to warm to 20 °C and stirred for 24 h, the solution color
became dark-red from red. The reaction solution was then filtered.
Crystallization at ꢀ20 °C afforded red crystals of 6 [16]. The yield
6 6
C D , 300 K, ppm): ꢀ77.8 (s, 1F), ꢀ121.9 (d, J = 8.46 Hz, 1F).
4
.3. Synthesis of complex 2
(
43%) of 1,2,4-trifluoro-benzene in reaction mixture was deter-
1
9
mined by F NMR spectra with trifluoromethyltoluene as the
external standard.
Complex 2 was synthesized according to the method given
above for complex 1.
Complex 2: Yield: 52.8%. m.p.: 102–104 °C. Anal. Calc. for
4
.8. Procedure for catalytic reaction
C
16
H
30CoF
2 3
OP (428.26 g/mol): C, 44.87; H, 7.06. Found: C, 45.03;
ꢀ1
H, 6.96%. IR (Nujol mull, cm ): 1881
m(C@O), 1591
m
(C@C), 938
), 6.47
, 300 K,
, 300 K, ppm): ꢀ124.0 (d,
3 4
In a 25 mL Schlenk tube containing a solution of CoMe(PMe )
1
q
(
(PMe
3
). H NMR (C
6
D
6
, 300 K, ppm): 0.92 (s, 27H, PMe
3
(
37.8 mg, 0.1 mmol) in 2 mL of THF were added to 2,4,5-tri-
flouro-benzaldehyde (1.6 mg, 1.0 mmol), then Et SiH (0.14 g,
.2 mmol) were added to the system. The reaction mixture was
stirred at 60 °C for 6 h. The yield of product was determined by
31
d, 2H, Ar–H), 7.22 (s broad, 1H, Ar–H); P NMR (C D
ppm): 18.3 (s, PCH ). F NMR (C D
3 6 6
6 6
3
1
9
1
J = 22.56 Hz, 1F), ꢀ88.6 (d, J = 19.74 Hz, 1F).
1
9
F NMR spectra using trifluoromethyltoluene as an external
4.4. Synthesis of complex 3
standard.
Complex 3 was synthesized according to the method given
4.9. X-ray crystal-structure determinations
above for complex 1.
Complex 3: Yield: 39.8%. m.p.: 98–100 °C. Anal. Calc. for C16
CoF OP (446.25 g/mol): C, 43.06; H, 6.55. Found: C, 43.18; H,
3 3
H
29
The single-crystal X-ray diffraction data of the complexes were
collected with a Bruker SMART Apex II CCD diffractometer