S.J. Sabounchei et al. / Journal of Organometallic Chemistry 692 (2007) 5440–5446
5441
2
P+Ar3
H
COPh (O)); 132.60 (d, JPC = 10.25 Hz, PPh3 (o)); 134.71
H
C
C
2
C
H
C
[M]
Ar3P
(COPh (p)); 139.15 (d, JPC = 14.69 Hz, COPh (i)); 182.84
O
C(O)R
P+Ar3
O
[M]
C
[M]
2
(d, JPC = 3.1 Hz, CO).
R
R
A1
A2
B
2.3.2. [(p-tolyl)3PCHC(O)C6H4Cl] (1b) [17]
O-co-ordination, cisoid O-co-ordination, transoid
C-co-ordination
Yield 0.406 g (89%), mp, 160–162 ꢁC. Anal. Calc. for
C29H26ClOP: C, 76.23; H, 5.74. Found: C, 76.29; H, 5.96.
IR (KBr, cmꢀ1) m: 1581 (C@O), 1522, 1497, 1485, 1402,
1382, 1186, 1103, 1087, 1077, 1011, 882 (P–C), 845, 813,
Scheme 1.
tively, using CDCl3 or DMSO-d6 as solvent. IR spectra
were recorded on a Shimadzu-U-04 FT-IR instrument
from KBr pellets. X-ray analysis was made on a STOE
IPDS-II diffractometer.
1
750, 718, 681, 649. H NMR (CDCl3) dH: 4.34 (d, 1H,
2JPH = 23.12 Hz, CH); 7.31–8.34 (m, 16H, arom.). 31P
NMR (CDCl3) dP: 13.15. 13C NMR (CDCl3) dC: 20.95
1
(CH3); 51.19 (d, JPC = 112.1 Hz, CH); 123.33 (d,
2.2. X-ray crystallography
1JPC = 93.56 Hz, p-tolyl (i)); 127.12 (COPh (m)); 127.88
3
(p-tolyl (p)); 129.10 (d, JPC = 12.66 Hz, p-tolyl (m));
2
A
colorless needle crystal with
a
dimension of
132.53 (d, JPC = 10.50 Hz, p-tolyl (o)); 134.27 (COPh
0.50 · 0.03 · 0.02 mm3 was mounted on a glass fiber and
used for data collection. All measurements were made on
a STOE IPDS-II diffractometer with graphite monochro-
mated Mo Ka radiation. Cell constants and an orientation
matrix for data collection were obtained by least-squares
refinement of diffraction data from 6660 unique reflections.
Data were collected at a temperature of 293(2) K to a max-
imum 2h value of 53.58 and in a series of x scans in 1ꢁ
oscillations and integrated using the STOE X-AREA soft-
ware package [12]. A numerical absorption correction was
applied using X-RED [13] and X-SHAPE [15] software’s.
The data were corrected for Lorentz and Polarizing effects.
The structure was solved by direct methods [14] and subse-
quent difference Fourier map and then refined on F2 by a
full-matrix least-squares procedure using anisotropic dis-
placement parameters [15]. All of hydrogen atoms were
located in a difference Fourier map and thereafter refined
isotropically. Subsequent refinements then converged with
R factors and parameters errors significantly better than
for all attempts to model the solvent disorder.
(p)); 139.71 (d, JPC = 14.91 Hz COPh (i)); 142.00 (d,
2
4JPC = 2.84 Hz COPh (o)); 182.31 (d, 2JPC = 3.58 Hz, CO).
2.3.3. [Ph3PCHC(O)C6H4NO2] (1c) [18]
Yield 0.374 g (88%), mp 182–184 ꢁC (lit. [18] 160–
162 ꢁC). Anal. Calc. for C26H20NO3P: C, 73.41; H, 4.74;
N, 3.29. Found: C, 73.12; H, 4.81; N, 3.53%. IR (KBr,
cmꢀ1) m: 1529 (C@O), 1481, 1437, 1408, 1390, 1341, 1318,
1180, 1104, 1083, 884 (P–C), 863, 750, 720, 693. 1H
2
NMR (CDCl3) dH: 4.51 (d, 1H, JPH = 22.85 Hz, CH);
7.34–7.94 (m, 19H, arom.). 31P NMR (CDCl3) dP: 14.19.
1
13C NMR (CDCl3) dC: 53.40 (d, JPC = 110.2 Hz, CH)
1
122.90 (COPh (m)); 126.05 (d, JPC = 91.28 Hz, PPh3 (i));
3
127.69 (PPh3 (p)); 128.91 (d, JPC = 12.46 Hz, PPh3 (m));
2
132.98 (d, JPC = 10.21 Hz, PPh3 (o)); 132.27 (COPh (o));
2
147.19 (d, JPC = 15.45 Hz, COPh (i)); 148.11 (COPh (p));
181.79 (s, CO).
2.3.4. [(p-tolyl)3PCHC(O)C6H4NO2] (1d) [17]
Yield 0.374 g (80%), mp, 156–158 ꢁC. Anal. Calc. for
C29H26NO3P: C, 74.51; H, 5.61; N, 3.00. Found: C,
74.21; H, 6.03; N, 3.33%. IR (KBr, cmꢀ1) m: 1600 (C@O),
1530, 1407, 1339, 1187, 1179, 1112, 886 (P–C), 862, 807,
2.3. Sample preparation
1
2.3.1. Preparation of [Ph3PCHC(O)C6H4Cl] (1a)
718, 718, 665, 656. H NMR (CDCl3) dH: 4.47 (d, 1H,
General procedure [16]: A solution of triphenylphosphine
(0.131 g, 0.5 mmol) and 2-bromo-40-chloroacetophenone
(0.117 g, 0.5 mmol) in acetone (15 mL) was stirred at room
temperature for 4 h. The resulting white precipitate was fil-
tered off, washed with diethylether and dried. Further
treatment with aqueous solution of NaOH (0.5 M,
50 mL) led to elimination of HBr, giving the free ligand
1a. Yield 0.372 g (90%), mp, 196–198 ꢁC. Anal. Calc. for
C26H20ClOP: C, 75.27; H, 4.86. Found: C, 75.42; H,
4.88%. IR (KBr, cmꢀ1) m: 1579 (C@O), 1522, 1480, 1435,
1404, 1383, 1188, 1175, 1104, 1085, 1009, 882 (P–C), 848,
747, 716, 693. 1H NMR (CDCl3) dH: 4.38 (d, 1H,
2JPH = 23.75 Hz, CH); 7.25–7.94 (m, 19H, arom.). 31P
NMR (CDCl3) dp: 14.19. 13C NMR (CDCl3) dc: 50.65 (d,
2JPH = 22.67 Hz, CH); 7.26–8.14 (m, 16H, arom.). 31P
NMR (CDCl3) dP: 13.13. 13C NMR (CDCl3) dC: 21.33
1
(CH3); 54.13 (d, JPC = 113.5 Hz, CH); 122.72 (COPh
(m)); 122.98 (d, 1JPC = 93.63 Hz, p-tolyl (i)); 127.55 (p-tolyl
3
(p)); 129.52 (d, JPC = 12.64 Hz, p-tolyl (m)); 132.84 (d,
4
2JPC = 10.52 Hz, p-tolyl (o)); 142.66 (d, JPC = 2.57 Hz
2
COPh (o)); 147.21 (d, JPC = 1.58 Hz COPh (i)); 147.87
(COPh (p)); 181.14 (s, CO).
2.3.5. Synthesis of [Ph3PCHC(O)C6H4Cl Æ Hg(NO3)2]
(2a)
General procedure: To a magnetically stirred solution of
Hg(NO3)2 Æ H2O (0.344 g, 1 mmol) in methanol (10 mL),
was added a methanolic solution (5 mL) of ylide 1a (0.414
g, 1 mmol). After 30 min the solvent was removed under
reduced pressure to 3 mL. After addition of diethylether
(30 mL) the white solid product was separated by filtration.
1
1JPC = 110.3 Hz, CH); 126.0 (d, JPC = 91.40 Hz, PPh3
(i)); 127.31 (COPh (m)); 128.03 (PPh3 (p)); 128.48 (d,
3JPC = 12.41 Hz, PPh3 (m)); 131.80 (d, JPC = 2.73 Hz,
4