Da Yang et al. / Chinese Journal of Catalysis 37 (2016) 405–411
407
stirred vigorously at room temperature for 3 h. The collected
Table 1
yellow solid precipitate was washed with diethyl ether and
dried under vacuum to give the product 2A with a yield of 86%.
A sample suitable for single‐crystal XRD analysis was obtained
Crystal data and structure refinement for 1A and 2A.
Item
1A
2A
Empirical formula
C36H28Cl2N6P2Pd1S2 C38H34Cl2N6P2Pd1S2
1
by slow volatilization of a CH2Cl2 solution containing 2A. H
2(C1F3S1O3)
Formula mass
Crystal system
Space group
a (nm)
848.00
Triclinic
P‐1
1176.21
Monoclinic
P21/c
NMR (δ, CD2Cl2): 9.93 (s, 2H, NCHN), 8.39 (t, 2H, J = 2 Hz), 8.04
(t, 2H, J = 2 Hz), 7.77–7.83 (m, 10H), 7.65–7.69 (m, 4H),
7.58–7.63 (m, 8H), 4.23 (s, 6H, 2CH3); 13C NMR (δ, CD3CN):
160.80 (s, NCN), 150.61 (s), 135.80 (s), 134.33 (t, J = 27 Hz),
132.54 (s), 132.19 (s), 128.99 (t, J = 22.5 Hz), 127.60 (q, J =
117.5 Hz, CF3), 125.22 (s), 122.40 (s), 120.73 (s), 36.77 (s, CH3);
31P NMR (δ, CD2Cl2): 11.8 (s, PPh2). CHN (%) elemental analysis
of 2A (C40H34Cl2F6N6O6P2Pd1S4, 1176.2): C 40.76, H 2.97, N 7.19
(Calcd. C 40.84, H 2.91, N 7.14).
1.02543(13)
1.16366(15)
1.6126(2)
81.525(4)
74.388(4)
83.266(4)
1.8269(4)
2
1.4322(2)
1.9177(3)
0.90143(13)
90
b (nm)
c (nm)
(o)
(o)
(o)
100.888(5)
90
V (nm3)
2.4313(6)
2
Z
2.2.3. Preparation of phosphine selenides
d
calc (Mg/m3)
1.542
1.607
Phosphine selenides were prepared by the reactions of
phosphines L1, L2, and PPh3 with 30 mg selenium (7.63% 77Se)
with a molar ratio of 1:1 in CDCl3 at 50 °C for 24 h. The seleni‐
des were directly analyzed without isolation by a Bruker
Avance 500 spectrometer at ambient temperature.
(Mo‐K) (mm)
T (°C)
0.892
0.803
23(2)
23(2)
(nm)
0.071073
20959
0.071073
28184
Total reflections
Unique reflections (Rint
R1 [I>2(I)]
)
6400 (0.0911)
0.0603
4288 (0.0821)
0.0417
0.0973
2.3. X‐ray crystallography
wR2 (all data)
0.1815
F(000)
856
1184
Goodness‐of‐fit on F2
0.995
1.038
Intensity data for 1A and 2A were collected at 25 °C on a
Bruker SMART APEX II diffractometer using graphite‐mono‐
chromated Mo‐K radiation ( = 0.071073 nm). Data reduction
included absorption correction by the multi‐scan method. The
structures were solved by direct methods and refined by
full‐matrix least‐squares using SHELXS‐97 (Sheldrick, 1990),
with all non‐hydrogen atoms refined anisotropically. Hydrogen
atoms were added at their geometrically ideal positions and
refined isotropically. The crystal data and refinement details
are given in Table 1.
washing the slurry with water (3 mL). The remaining IL phase
was then collected for reuse. Because of the stoichiometric
consumption of the base, Et3N (7.5 mmol) was added to each
reaction. All manipulations were conducted in air.
2.5. 1H and 13C NMR data for the products listed in Table 3
1,3‐Diphenylprop‐2‐yn‐1‐one (Table 3, entry 1). 1H NMR (δ,
CDCl3): 8.23 (d, 2H, J = 7.2 Hz), 7.65–7.68 (m, 2H), 7.59–7.63 (m,
1H), 7.45–7.52 (m, 3H), 7.38–7.42 (m, 2H); 13C NMR (δ, CDCl3):
178.08 (s, C=O), 136,89 (s), 134.18 (s), 133.12 (s), 130.85 (s),
129.62 (s), 128.73 (s), 128.67 (s), 120.14 (s), 93.16 (s), 86.91
(s).
3‐Phenyl‐1‐(o‐tolyl)prop‐2‐yn‐1‐one (Table 3, entry 2). H
NMR (δ, CDCl3): 8.31 (d, 2H, J = 8.8 Hz), 7.65–7.67 (m, 2H),
7.35–7.49 (m, 5H), 7.28 (d, 1H, J = 7.2 Hz), 2.68 (s, 3H, CH3); 13
2.4. General procedure for carbonylative Sonogashira reaction
In a typical experiment, the isolated crystalline precatalyst
1A (or 2A, 0.005 mmol) was sequentially mixed with 3 mL of
solvent (DMF or [Bmim]PF6 if required), iodobenzene (5
mmol), phenylacetylene (6 mmol), and Et3N (7.5 mmol). The
obtained mixture was placed in a sealed Teflon‐lined stainless
steel autoclave, purged with syngas (CO, 1.0 MPa) and then
stirred vigorously at the required temperature for the ap‐
pointed time. Upon completion of the reaction, the mixture was
cooled to room temperature and the pressure was carefully
released. The reaction mixture was extracted with diethyl ether
(5 mL 3). The ether fractions were combined and then ana‐
lyzed by GC to determine the conversion of PhI (1‐dodecane as
an internal standard) and the selectivity for the carbonylative
products (normalization method). The structures of the car‐
bonylative products were further confirmed by GC‐MS.
1
C
NMR (δ, CDCl3): 179.78 (s, C=O), 140.54 (s), 140.54 (s), 135.70
(s), 133.24 (s), 132.96 (s), 132.21 (s), 130.63 (s), 128.67 (s),
125.92 (s), 120.35 (s), 91.87 (s), 88.38 (s), 22.02 (s, CH3).
1
3‐Phenyl‐1‐(m‐tolyl)prop‐2‐yn‐1‐one (Table 3, entry 3). H
NMR (δ, CDCl3): 8.04 (t, 2H, J = 6.8 Hz), 7.68–7.70 (m, 2H),
7.39–7.51 (m, 5H), 2.45 (s, 3H, CH3); 13C NMR (δ, CDCl3): 178.28
(s, C=O), 138.53 (s), 136.91 (s), 135.03 (s), 133.09 (s), 130.79
(s), 129.81 (s), 128.71 (s), 128.55 (s), 127.16 (s), 120.22 (s),
92.91 (s), 87.03 (s), 21.38 (s, CH3).
1
3‐Phenyl‐1‐(p‐tolyl)prop‐2‐yn‐1‐one (Table 3, entry 4). H
In the recycling experiments, the remaining slurry contain‐
ing 2A, [Bmim]PF6, and the formed ammonium salt (Et3NHI)
after ether extraction was used directly without further treat‐
ment for the next run unless otherwise specified. In specified
cases, the formed ammonium salt (Et3NHI) was removed by
NMR (δ, CDCl3): 8.12 (d, 2H, J = 8 Hz), 7.67–7.70 (m, 2H),
7.47–7.51 (m, 1H), 7.40–7.44 (m, 2H), 7.32 (d, 1H, J = 8 Hz),
2.45 (s, 3H, CH3); 13C NMR (δ, CDCl3): 177.78 (s, C=O), 145.26
(s), 134.61 (s), 133.07 (s), 130.72 (s), 129.75 (s), 129.38 (s),