K. Karami et al. / Journal of Organometallic Chemistry 781 (2015) 35e46
45
C6H4, both isomers),129.77 (s, C4, C6H4, both isomers),129.85 (s, Cm,
C6H4CO, isomer A), 129.94 (s, Cm, C6H4CO, isomer B), 130.22 (s, C3,
C6H4, both isomers), 130.75 (s, Cp, PPh2, both isomers), 131.48 (s, Co,
C6H4CO, isomer B), 131.54 (s, Co, C6H4CO, isomer A), 133.03 (s, Cp,
C6H4CO, isomer A), 133.11 (s, Cp, C6H4CO, isomer A), 133.49 (s, Co,
PPh2, isomer B), 133.57 (s, Co, PPh2, isomer A), 136.40 (s, C1, C6H4,
isomer A), 136.48 (s, C1, C6H4, isomer B), 149.71 (s, Co, 4-MePy, both
isomers), 150.51 (s, Cp, 4-MePy, both isomers), 152.41 (s, Cm, 4-
MePy, both isomers); 31P{1H} NMR (202.5 MHz, CDCl3, ppm):
[Pd2Cl2{k
2(C,C)-[(C6H4-2)PPh2]CH(CO)C6H4Ph-4}2(dppp)], 3b
To the solution of 0.124 g (0.1 mmol) complex 3 in CHCl3 (10 mL),
bis(diphenylphosphino)propane (dppp) (0.041 g, 0.1 mmol) was
added, and the resulting solution was stirred for 3 h at room
temperature (RT). After that, the solvent was evaporated and the
residue was treated with 15 mL CH2Cl2/n-hexane (1:3) to give 3b as
the yellow solid.
Yield (82%), M.p. 164 ꢁC (dec.), IR (KBr, cmꢀ1);
NMR (400 MHz, CDCl3, ppm):
n
(CO) ¼ 1621,1H
d
¼ 2.00e2.70 (m, CH2 (dppp)), 4.54,
d
¼ 15.89.03 (s, 1P, CHP, isomer A), 20.35 (s, 1P, CHP, isomer B).
5.41 (m, CHP, meso-rac), 6.57, 6.91, 7.06, 7.20, 7.37, 7.45, 7.53, 7.63,
7.82, 7.92, 8.52 (m, C6H4, C6H4CO, PPh2, meso-rac); 31P{1H} NMR
(161.97 MHz, CDCl3, ppm):
24.33, 25.02, 25.22 (dppp and CHP, meso-rac isomers).
d
¼ ꢀ2.76, ꢀ2.55, 11.22, 13.66, 24.09,
[PdCl{
k
2(C,C)-[(C6H4-2)PPh2]CH(CO)C6H4F-4}(Py)], 1d
To the solution of 0.108 g (0.1 mmol) complex 1 in CH2Cl2
(10 mL), pyridine (Py) (16 L, 0.2 mmol) was added and the solution
m
DFT calculations
was stirred for 30 min at room temperature (RT). After 1 h, the
solvent was evaporated and the residue was treated with cold n-
hexane (15 mL) to give 1d as the yellow solid.
All of the theoretical calculations were performed using the
Gaussian 09 computational package [42].
Yield (78%), M.p.189 ꢁC, Anal. Calc for C31H24NClFOPPd: C, 60.21;
H, 3.91; N, 2.27. Found. C, 60.37; H, 3.86; N, 2.25; IR (KBr, cmꢀ1);
n
X-ray structure determinations
(CO) ¼ 1625, 1H NMR (500 MHz, CDCl3, ppm):
d
¼ 5.02 (s, 1H, CHP,
isomer A), 5.11 (d, 1H, CHP, 2JHP ¼ 4.1 Hz, isomer B), 6.51 (d, 1H, H6,
C6H4, 3JHP ¼ 7.0 Hz, isomer A), 6.81e6.87 (m, 4H, H4 þ H5, C6H4, both
isomers), 6.93 (m, 1H, Hp, py, isomer A), 7.01 (m, 1H, Hp, py, isomer
B), 7.04 (m, 1H, H6, C6H4, isomer B), 7.06 (m, 2H, H3, both isomers),
7.16 (m, 2H, Hm, py, isomer A), 7.22 (m, 2H, Hm, Py, isomer B), 7.32
(m, 2H, Ho, py, isomer A), 7.40 (m, 2H, Ho, py, isomer B), 7.47e7.82
(20H, PPh2, both isomers), 8.20 (m, 2H, C6H4CO, isomer A),
8.30e8.37 (m, 2H, C6H4CO, isomer B), 8.47 (m, 2H, C6H4CO, isomer
A), 8.52 (m, 2H, C6H4CO, isomer B); 31P{1H} NMR (202.5 MHz,
The data collection was performed at room temperature using
the X-scan technique and the STOE X-AREA software package [46].
The crystal structures were solved by direct methods and refined by
full-matrix least-squares on F2 by SHELXL97 [47] and using the
ORTEP-3 crystallographic software package [48]. All non-hydrogen
atoms were refined anisotropically using reflections I > 2r (I).
Hydrogen atoms were inserted at calculated positions using a
riding model with fixed thermal parameters.
CDCl3, ppm):
isomer B).
d
¼ 15.86 (s, 1P, CHP, isomer A), 20.38(s, 1P, CHP,
General experimental procedure for the Suzuki cross-coupling
reaction
[PdCl{
To the solution of 0.108 g (0.1 mmol) complex 1 in CH2Cl2
(10 mL), piperidine (PiPe) (20 L, 0.2 mmol) was added and the
k
2(C,C)-[(C6H4-2)PPh2]CH(CO)C6H4F-4}(PiPe)], 1e
Typical experimental procedure was carried out for the Suzuki
cross-coupling reaction under air atmosphere. A reaction tube was
charged with Pd catalyst (0.1 mol%), aryl bromide (0.5 mmol), aryl
boronic acid (0.75 mmol), Solvent (6 mL), bases (1.5 mmol). The
mixture was refluxed for 1 h (75 ꢁC). Then the mixture was filtered
with silica gel and used for TLC. After the reaction was completed, if
the reaction's conversion wasn't completed we used GC. The sol-
vent was evaporated under reduced pressure to provide a white
solid; the pure product was prepared via dissolving the white solid
and again precipitating with dichloromethane and n-hexane and
dried under reduced pressure.
m
solution was stirred for 30 min at room temperature (RT). After 1 h,
the solvent was evaporated and the residue was treated with cold
n-hexane (15 mL) to give 1e as the green solid.
Yield (84%), M.p.189 ꢁC, Anal. Calc for C31H30NClFOPPd: C, 59.63;
H, 4.84; N, 2.24. Found. C, 59.59; H, 4.80; N, 2.25; IR (KBr, cmꢀ1);
n
(CO) ¼ 1620,
n
(NH) ¼ 3411; 1H NMR (500 MHz, CDCl3, ppm):
d
¼ 1.24e3.12 (m, 11H, PiPe, both isomers), 4.85 (s, 1H, CHP, isomer
A), 4.96 (d, 1H, CHP, 2JHP ¼ 4.4 Hz, isomer B), 6.82 (t, H3 þ H6, C6H4,
isomer A), 7.03 (t, 2H, H4 þ H5, C6H4, 3JHH ¼ 9.2 Hz, isomer B), 7.15 (t,
3
2H, H4 þ H5, JHH ¼ 9.2 Hz, isomer A), 7.21 (m, 2H, H3 þ H6, C6H4,
Conclusion
isomer B), 7.35e7.78 (10H, PPh2, both isomers), 8.08 (dd, 2H,
C6H4CO, isomer B), 8.15e8.28 (m, 4H, C6H4CO, isomer A), 8.44 (dd,
2H, C6H4CO, isomer B); 31P{1H} NMR (202.5 MHz, CDCl3, ppm):
In this work, the synthesis and characterization of cyclo-
palladated complexes of phosphorus ylides containing nitrogen,
phosphorus or bridging diphosphine ligands have been investi-
gated. The presence of intermolecular interactions in some new
complexes which were structurally determined, lead to supramo-
lecular structures. Overall, these organopalladated (II) complexes
have considerable potential as building blocks through their poly-
mer, sheet or network supramolecular structures.
According to the theoretical calculations for the synthesized
complexes 1, 1a and 2a, there are very good agreements between
the calculated bond lengths and angles and those obtained from the
experiment. The vibrational frequencies obtained theoretically for
the stretching of C]O bond for each three synthesized complexes,
are very close to the experimental value reported in this work.
Theoretical data for structure 1 fully confirmed the more stability of
the trans isomer.
d
¼ 13.86 (s, 1P, CHP, isomer A), 17.59 (s, 1P, CHP, isomer B).
[Pd2Cl2{
k
2(C,C)-[(C6H4-2)PPh2]CH(CO)C6H4Ph-4}2(dppe)], 3a
To the solution of 0.124 g (0.1 mmol) complex 3 in CHCl3 (10 mL),
bis(diphenylphosphino)ethane (dppe) (0.040 g, 0.1 mmol) was
added, and the resulting solution was stirred for 3 h at room
temperature (RT). After that, the solvent was evaporated and the
residue was treated with 15 mL CH2Cl2/n-hexane (1:3) to give 3a as
the yellow solid.
Yield (85%), M.p. 178 ꢁC (dec.), IR (KBr, cmꢀ1);
NMR (400 MHz, CDCl3, ppm):
n
(CO) ¼ 1621,1H
d
¼ 1.94e2.83 (m, CH2 (dppe)), 5.00,
5.60 (m, CHP, meso-rac), 6.17, 6.46, 6.83, 7.19, 7.34, 7.45, 7.57, 7.61,
7.66, 7.73, 7.89, 7.92, 8.02, 8.04, 8.14, 8.59 (m, C6H4, C6H4CO, PPh2,
meso-rac); 31P{1H} NMR (161.97 MHz, CDCl3, ppm):
d
¼ 12.34,17.89,
24.09, 30.60, 32.04, 43.43, 52.48, 63.84 (dppe and CHP, meso-rac
isomers).
The binuclear chloro-bridged cyclopalladated complex of
phosphorus ylide (1) and two mononuclear phosphine palladium