Synthesis and application of ortho-palladated complex of (4-phenylbenzoylmethylene)triphenylphosphorane as a highly active catalyst in the Suzuki cross-coupling reaction

Article abstract of DOI:10.1016/j.jorganchem.2010.10.025

The ortho-metallated complex [Pd(μ-Cl){κ₂(C,C)-[C ₆H₄(PPh₂CHC(O)C₆H ₄-Ph-4)}]₂ (2a) was prepared by refluxing of Pd(OAc) ₂ and {(Ph)₃PCHCOC₆H₄-Ph-4} (PhBPPY) of in CH₂Cl₂ followed by addition of an excess of KCl in MeOH Complex (2a) reacts with triphenylphosphine to give the mononuclear derivative [Pd(Cl)(PhC₆H₄COCHPPh₂C ₆H₄)(PPh₃)] (3a) whose crystal structure has been determined by single crystal X-ray diffraction. The Suzuki reactions of aryl bromides and chlorides of varying electron density using complex (3a) as an efficient catalyst were performed, giving the cross-coupling products in good to excellent yields.

Full text of DOI:10.1016/j.jorganchem.2010.10.025

Journal of Organometallic Chemistry 696 (2011) 940e945
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and application of ortho-palladated complex of
(4-phenylbenzoylmethylene)triphenylphosphorane as a highly
active catalyst in the Suzuki cross-coupling reaction
,
b
a
Kazem Karami a , Corrado Rizzoli , Mina Mohamadi Salah
*
a Department of Chemistry, Isfahan University of Technology, Isfahan 84156/83111, Iran
b Department of General and Inorganic Chemistry, University of Parma, Parma, Italy
a r t i c l e i n f o
a b s t r a c t
Article history:
The ortho-metallated complex [Pd(
m
-Cl){k2(C,C)-[C6H4(PPh2CHC(O)C6H4-Ph-4)}]2 (2a) was prepared by
Received 26 July 2010
Received in revised form
11 October 2010
Accepted 14 October 2010
Available online 23 October 2010
refluxing of Pd(OAc)2 and {(Ph)3PCHCOC6H4-Ph-4} (PhBPPY) of in CH2Cl2 followed by addition of an
excess of KCl in MeOH Complex (2a) reacts with triphenylphosphine to give the mononuclear derivative
[Pd(Cl)(PhC6H4COCHPPh2C6H4)(PPh3)] (3a) whose crystal structure has been determined by single
crystal X-ray diffraction. The Suzuki reactions of aryl bromides and chlorides of varying electron density
using complex (3a) as an efficient catalyst were performed, giving the cross-coupling products in good to
excellent yields.
Keywords:
Ó 2010 Elsevier B.V. All rights reserved.
Ortho-metallated complexes
Palladium catalyst
Suzuki cross-coupling
1. Introduction
2. Results and discussion
Palladium-catalyzed Suzuki cross-coupling reactions of aryl
halides with aryl boronic acids have recently emerged as an
extremely efficient and important tool in organic synthesis, as well
as in a variety of industrial processes [1e12]. The key advantages of
the Suzuki coupling compared to other coupling methods [13e15]
are the mild reaction condition and the commercial availability of
the diverse boronic acids that are environmentally safer than the
other organometallic reagents [16,17]. In addition, the handling
and removal of boron-containing byproducts is easy when com-
pared to other organometallic reagents, especially in a large-scale
synthesis [18].
As part of our ongoing study aimed on the synthesis of new
palladium catalysts, the ortho-palladated complex of (4-phenyl-
benzoylmethylene)triphenylphosphorane [Pd(Cl)(PhC6H4COCHP-
Ph2C6H4)(PPh3)] (3a) has been prepared and its structure elucidated
by single crystal X-ray analysis. The complex demonstrated to be an
efficient catalyst in Suzuki cross-coupling reactions of phenyl
boronic acid with aryl halides, resulting in good to excellent yields of
the desired products.
The synthesis pathway starting from the (4-phenylbenzoyl-
methylene)triphenylphosphorane (PhBPPY) (1a) and leading to the
formation of the dimeric complex (2a) and, finally, to the triphenyl-
phosphine mononuclear adduct (3a) is shown in Scheme 1.
The reaction of an equimolar amount of Pd(OAc)2 (OAc ¼ acetate)
with PhBPPY in refluxing CH2Cl2 and further reaction of the acetate
intermediate with excess NaCl in methanol gives a insoluble solid,
whose stoichiometrycorresponds tothe ortho-metallated complexes
[Pd(m-Cl){C,C-[C6H4(PPh2CHC(O)C6H4-4-Ph)}]2 (2a). As already re-
ported for similar compounds [19e22], (2a) reacts with triphenyl-
phosphine to give the mononuclear palladium (II) derivative [Pd(Cl)
(PhC6H4COCHPPh2C6H4)(PPh3)] (3a).
2.1. Structure analysis of the catalyst
In the ortho-palladated complex (3a) (Fig. 1), one phenyl ring of
the triphenylphosphine group of the PhBPPY ligand has undergone
a CeH bond activation process, leading to the endo metallation of
the phosphorus ylide. The palladium(II) atom is coordinated by
a ylidic carbon atom (C1), a metallated carbon atom (C15), a chlo-
ride anion (Cl1) and a phosphorus atom (P2) of a PPh3 ligand in
a distorted square-planar geometry. The extent of the distortion
from the regular geometry may be evinced from the values of the
* Corresponding author. Tel.: þ98 3113912351; fax: þ98 3113912350.
E-mail address: karami@cc.iut.ac.ir (K. Karami).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.10.025

K. Karami et al. / Journal of Organometallic Chemistry 696 (2011) 940e945
941
Scheme 1. (i) Pd(OAc)2/CH2Cl2/reflux (60 ꢀC) 24 h; (ii) NaCl/MeOH, r. t; (iii) PPh3/CH2Cl2.
bond angles subtended at the metal centre (84.81(10)e177.13 (8)ꢀ;
Table 1). These values are in good agreement with those observed
in closely related complex [PdCl(PhBPPY)(4-picoline)] (83.5(3)e
176.76(16)ꢀ [22]).
(sp3) coupling by reacting benzyl bromide (entry 6) with phenyl
boronic acid, which afforded the coupling product in excellent yields.
Thus the catalyst afforded average to excellent yields of the biaryl
products at 60 ꢀC. In the literature, only a few catalysts are known for
effecting the Suzuki cross-coupling reactions under mild conditions
[10,26e33].
The Pd1eC15 bond distance (2.008(3) Å) involving the ortho-
metallated carbon atom is not significantly different from those
found in the analogous 4-picoline complex (2.002(6) Å) and in
related ortho-palladated complexes (1.990(4) Å [20]; 1.9997(4) Å
[23]), while the Pd1eC1 bond distance involving the ylide carbon
atom (2.180(2) Å) in complex (3a) is longer (2.101(6) Å [22]; 2.090
(3) Å [23]). The difference observed between the Pd1eC1 and
Pd1eC15 bond lengths in 3a possibly reflecting the different trans
effects of the phosphorus and chlorine atoms. The stabilized reso-
nance structure for the parent ylide is destroyed due to the complex
formation, thus the C1eC2 bond length (1.467(4) Å) in complex 3a
were significantly longer than the corresponding distances found in
the similar uncomplexed phosphoranes (1.401(2) Å [24] and 1.407
(8) Å [25]). The P1eC1 bond length (1.777(3) Å) is identical, within
experimental error, to that reported for the 4-picoline complex
(1.775(6) Å [24]). The Pd1/C15/C20/P1/C1 five-membered ring met-
allacycle adopts an envelope conformation, with atom C1 displaced
by (1.058(3) Å) from the meanplane of the remaining four atoms. The
conformation of the complex molecule is stabilized by intra-
molecular CeH.Cl and CeH.O hydrogen bonds: C4eH4 ¼ 0.93 Å,
H4.Cl1 ¼ 2.64 Å, C4.Cl1 ¼ 3.518(3) Å, C4eH4.Cl1 ¼ 158ꢀ;
C28eH28 ¼ 0.93 Å, H28.O1 ¼ 2.40 Å, C28.O1 ¼ 3.098(2) Å,
C28eH28.O1 ¼ 132ꢀ.
2.3. SuzukieMiyaura coupling reactions of aryl chlorides
The cross-coupling of aryl chlorides with phenyl boronic acid in
the presence of 0.01 mmol of catalyst were carried out at 60 ꢀC
using MeOH as solvent (Table 2). Electron deficient substrates such
as chlorobenzene, 4-chloronitrobenzene, and benzyl chloride
(entries 1, 7, and 8, respectively) coupled with phenyl boronic acid
with yields of the coupling products ranging from 72 to 97%.
2.4. Comparison of aryl bromide and aryl chloride reaction
The main drawback of the Pd-mediated Suzuki cross-coupling
reaction is that only aryl iodides and aryl bromides can be used
efficiently. Recent progress on increasing the reaction rate of aryl
chlorides permitted to overcome this problem [34e40]. The
stronger CeCl bond is in fact responsible of the slower reaction rate
of aryl halides, because the oxidative addition step was suggested to
be the rate determining step in cross-coupling catalytic cycles [41].
3. Experimental section
2.2. SuzukieMiyaura coupling reactions of aryl bromides
3.1. X-ray crystallography
A series of aryl and benzyl bromides (Table 2) were coupled with
phenyl boronic acid with 0.01 mmol of catalyst at 60 ꢀC under
optimized reaction conditions. In the presence of electron with-
drawing substituents (entries 2, 11) as well as in the case hetero-
cyclic derivative (entry 12) the reaction afforded excellent yields of
coupling products at 60 ꢀC.
The couplingof 3-bromotoluene(entry3), 2-bromobenzaldehyde
(entry 4), 2-bromonaphtalene (entry 5), 3-chlorobromobenzene
(entry 9), 2-chlorobromobenzene (entry 10) and 2-bromoni-
trobenzene (entry 13) with phenyl boronic acid resulted in good
yields at 60 ꢀC. The Suzuki coupling was also extended to C(sp2)-C
Single crystals of (3a) suitable for X-ray crystallography were
obtained by diffusion of n-hexane into a CH2Cl2 solution of the
complex. Intensity data were collected at ambient temperature (294
(2) K) using graphite monochromated Mo
Ka
radiation
(
l
¼ 0.71073 Å) on a Bruker SMART 1000 CCD diffractometer. Data
were corrected for absorption using the SABABS program [42]. All
non-hydrogen atoms were refined anisotropically. All H atoms were
placed in calculated positions and treated as riding on their parent
atoms, with CeH ¼ (0.93e0.98 Å), and with Uiso(H) ¼ 1.2 Ueq(C).
Crystallographic data and parameters concerning data collection
and structure solution and refinement are summarized in the

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K. Karami et al. / Journal of Organometallic Chemistry 696 (2011) 940e945
Fig. 1. The molecular structure of 3a. Displacement ellipsoids are drawn at the 40% probability level. Hydrogen atoms are omitted for clarity.
Supplementary data, selected bond lengths (Å) and angles (ꢀ) are
listed in Table 1. An ORTEP-3 [43] diagram of the complex molecule
is shown in Fig. 1, a view of the unit-cell content is given in the
Supplementary data.
gel fluorescent 254 nm (0.2 mm) were used for monitoring the
reaction progresses. 1H NMR (500 MHz), 13C NMR (125 MHz), and
31P NMR (202 MHz) spectra were recorded in CDCl3 solutions at
room temperature (TMS was used as an internal standard) on
a Bruker Avance spectrometer. The cross-coupling products were
characterized by their 1H NMR spectra and melting points.
3.2. Materials and techniques
3.3. General procedure for the synthesis of the Pd complex (3a):
[Pd(Cl)(PhC6H4COCHPPh2C6H4)(PPh3)]
All chemicals were purchased from Fluka and Merck companies.
Gas chromatography carried out with a Shimadzu GC 14-A gas
chromatograph and thin layer chromatography on precoated silica
To a solution of Pd(OAc)2 (0.116 g, 0.52 mmol) in CH2Cl2 (15 ml)
(4-phenylbenzoylmethyl)triphenylphosphorane (PhBPPY) (0.237 g,
0.52 mmol) (1a) was added. The mixture was refluxed for 24 h at
60 ꢀC. The mixture was then evaporated to dryness and MeOH was
added to the solid and the green suspension treated with an excess
of NaCl (0.111 g, 1.034 mmol) at room temperature. A yellow
suspension immediately produced and stirring was maintained for
12 h at room temperature, after which the precipitate was filtered,
washed with Et2O (5 ml) and water (10 ml) and dried in vacuum to
Table 1
Selected bond lengths (Å) and angles (ꢀ) for complex 2a.
Pd(1)eP(2) 2.9316(7)
Pd(1)eCl(1) 2.4058(7)
Pd(1)eC(1) 2.180(2)
Pd(1)eC(15) 2.008(3)
P(2)eC(39) 1.826(3)
P(1)eC(1) 1.777(3)
P(1)eC(27) 1.810(3)
P(1)eC(20) 1.782(3)
P(1)eC(21) 1.800(3)
C(1)eC(2) 1.467(4)
C(2)eO(1) 1.226(3)
C(2)eC(3) 1.507(4)
P(2)eC(33) 1.847(3)
P(2)eC(45) 1.823(3)
obtain [Pd(m-Cl){C,C-[C6H4(PPh2CHC-(O)C6H4-4-X)}]2 (2a).To a
C(15)ePd(1)eP(2) 95.18(8)
Cl(1)ePd(1)eP(2) 86.97(3)
C(15)ePd(1)eC(1) 84.81(10)
Cl(1)ePd(1)eC(1) 92.85(7)
C(15)ePd(1)eCl(1) 177.13(8)
C(1)ePd(1)eP(2) 173.87(7)
C(15)ePd(1)eP(1) 61.15(8)
C(1)ePd(1)eP(1) 37.13(7)
P(2)ePd(1)eP(1) 138.22(2)
Cl(1)ePd(1)eP(1) 115.99(2)
suspension of (2a) (0.1194 g, 0.1 mmol) in CH2Cl2 (15 mL) was added
PPh3 (0.0524 g, 0.2 mmol). The initial yellow suspension gradually
dissolved after stirring for 8 h at room temperature. The resulting
solution was filtered over a CeliteÓ pad to remove any residual

K. Karami et al. / Journal of Organometallic Chemistry 696 (2011) 940e945
943
Table 2
Reactants and products of the Suzuki cross-coupling reactions.a
Entry
Aryl halide
Product
Yield (%)b
1
2
97
100
3
4
78
91
5
84
6
7
8
100
72
77
9
85
84
10
11
12
100
96
13
81
Reaction conditions: aryl halide (0.5 mmol), PhB(OH)2 (0.75 mmol), [Pd(Cl)(PhBPPY)(PPh3)] (0.01 mmol), Na2CO3 (1.5 mmol), MeOH (6 ml), Reflux 60 ꢀ C, 40 min.
GC yields, ꢁ2%.
a
b

944
K. Karami et al. / Journal of Organometallic Chemistry 696 (2011) 940e945
insoluble solid. The clear solution obtained and was evaporated to
dryness, and the treatment of the residue with Et2O (30 mL) gave [Pd
(Cl)(PhBPPY)(PPh3)] (3a) as a yellow solid.
3.5.6. 4-Nitro-biphenyl
IR (KBr):
: 3077, 1598, 1515, 1345, 1105, 854, 740, 697. 1H NMR
(300 MHz, CDCl3, ppm):
¼ 8.29 (d, J(HeH) ¼ 8.7 Hz, 2H), 7.73 (d, J
y
d
M.p. 146 ꢀC; Yield (0.1014 g, 59%); Anal. Calc for C50H39OP2PdCl:
(HeH) ¼ 8.7 Hz, 2H), 7.62 (dd, J(HeH) ¼ 8.4, 1.5 Hz, 2H), 7.52e7.41
C, 65.86; H, 4.27; Found. C, 65.39; H, 4.0; IR (KBr, cmꢂ1):
n
(C]O):
(m, 3H). 13C NMR (75 MHz, CDCl3, ppm):
129.3, 129.0, 127.9, 127.5, 124.2 [47].
d
¼ 147.7, 147.2, 138.9,
1619. 1H NMR (500 MHz, CDCl3, ppm);
d
¼ 5.5 (s, 1H, CHP), 6.5 (s,
2H, C6H4 3J(HeH) ¼ 3 Hz), 6.90 (m, 1H, C6H4, 3J(HeH) ¼ 4 Hz), 7.19
(m, 6H, Hm, PPh3), 7.32 (m, 6H, Hm, PPh2 þ Hm, C6H5), 7.44 (m, 6H,
Hp, C6H5 þ PPh2 þ PPh3), 7.6 (m, 6H, Ho, PPh3), 7.66 (m, 2H, Hm,
C6H4CO), 7.88 (m, 2H, Ho, C6H5), 8.02 (m, 2H, Ho, PPh2), 8.29 (m, 2H,
3.5.7. 3-Chloro-biphenyl
A yellow solid, M.p. 44.5e47.5 ꢀC; IR (KBr):
y
: 3057, 3033, 2924,
1380, 1494, 1464, 1425, 1130, 1072, 1038, 1011, 771, 746, 697; 1H
Ho, PPh2), 8.31 (d, 2H, Ho, C6H4CO, JHH ¼ 7.1 Hz). 31P{1H} NMR
NMR (300 MHz, CDCl3, ppm):
1H, ArH) [44].
d
¼ 7.37e7.55 (m, 8H, ArH), 8.01 (d,
3
(CDCl3):
d
¼ 15.06 (s, CHP), 31.86 (s, Pd-PPh3). 13C{1H} NMR:
1
2
d
¼ 40.47 (dd, CHP, JPC ¼ 63.13 Hz, JPC ¼ 21 Hz), 123.72 (d, C1,
1JPC ¼ 13.20 Hz), Caromatic
{d
¼ 126.71, 127.46, 128.12 (d, Co PPh2 or Co
3.5.8. 2-Chloro-biphenyl
PPh3, 2JPC ¼ 10.19 Hz), 129.08 (d, Cm PPh2, 3JPC ¼ 6.03 Hz), 129.68 (d,
A yellow solid, M.p. 32.5e33.5 ꢀC; IR (KBr):
y
: 3059, 3031, 2924,
2
Ci PPh2, JPC ¼ 11.82 Hz), 130.02, 130.53, 130.66, 131.72, 132.84,
1380, 1498, 1467, 1425, 1128, 1075, 1036, 1009, 770, 748, 699; 1H
134.64, 138.06, 139.2, 140.8, 144.2},
d
¼ 133.31 (d, C3, 3JPC ¼ 9.31 Hz),
NMR (300 MHz, CDCl3, ppm):
d
¼ 7.24e7.61 (m, 9H, ArH) [44].
d
¼ 135.16 (d, Ci PPh3, 2JPC ¼ 11.82 Hz) [22].
3.5.9. 4-Methoxy-biphenyl
IR (KBr):
(300 MHz, CDCl3, ppm):
y
: 3020, 1612, 1519, 1487, 1216, 909, 759. 1H NMR
3.4. General experimental procedure for Suzuki cross-coupling
reactions
d
¼ 7.56e7.51 (m, 4H), 7.41 (t, J(HeH)
¼ 7.5 Hz, 2H), 7.29 (t, J(HeH) ¼ 7.5 Hz, 1H), 6.98 (d, J(HeH) ¼ 7.5 Hz,
2H), 3.85 (s, 3H). 13C NMR (75 MHz, CDCl3, ppm):
133.9, 128.9, 128.3, 126.9, 126.8, 114.3, 55.4 [47].
d
¼ 159.3, 140.9,
A mixture of an aryl halide (0.5 mmol), phenyl boronic acid
(0.75 mmol), [Pd(Cl)(PhBPPY)(PPh3)] (0.01 mmol), Na2CO3
(1.5 mmol), and MeOH (6 ml) was heated to 60 ꢀC for 40 min under
reflux. The reaction mixture was then cooled to room temperature
and the solvent was removed under reduced pressure. The
combined organic extracts were washed with brine and dried over
MgSO4. The solvent was evaporated and a crude product was
obtained. A small aliquot of the reaction mixture was diluted in
MeOH for direct GC analysis.
3.5.10. 2-Phenylpyridine
1H NMR (500 MHz, CDCl3, ppm):
1H), 7.98 (d, J(HeH) ¼ 7.5 Hz, 2H), 7.75 (m, 2H), 7.48 (t, J(HeH) ¼
5.0 Hz, 2H), 7.42 (d, J(HeH) ¼ 7.5 Hz, 1H), 7.24 (d, J(HeH) ¼ 5.5 Hz,
1H) [49].
d
¼ 8.70 (d, J(HeH) ¼ 4.5 Hz,
3.5.11. 2-Nitro-biphenyl
The aryl halides employed in the Suzuki cross-coupling reac-
tions with phenyl boronic acid and the coupling products are listed
in Table 2.
1H NMR (500 MHz, CDCl3, ppm):
1H), 7.60 (m, 1H), 7.44 (m, 5H), 7.31 (m, 2H) [49].
d
¼ 7.84 (q, J(HeH) ¼ 2.5 Hz,
4. Conclusion
3.5. Characterization of the products of Suzuki cross-coupling
reactions
In this paper, the synthesis and characterization is reported of
a highly active and efficient catalyst for promoting the Suzuki cross-
coupling reaction of various aryl halides to produce the corre-
sponding products in average to excellent yields. The ease of
preparation of the complex, its high solubility in organic solvents,
indefinite shelf life, and stability toward air make it an ideal
complex for the above transformations.
3.5.1. Biphenyl
A white solid, M.p. 70.5e72.0 ꢀC; IR (KBr):
y
: 3037, 1569, 1480,
1429, 729, 697; 1H NMR (300 MHz, CDCl3, ppm):
d
¼ 7.35e7.37 (m,
2H, ArH), 7.4e7.5 (m, 4H, ArH), 7.6e7.6 (m, 4H, ArH) [44].
3.5.2. 3-Methylbiphenyl
Acknowledgement
M.p. 30e34 ꢀC; 1H NMR (300 MHz, CDCl3, ppm):
d
¼ 7.7 (m, 2H),
7.5 (m, 6H), 7.3 (m, 1H), 2.5 (s, 3H) [45].
The authors acknowledge the Department of Chemistry Isfahan
University of Technology, Isfahan, Iran and, Department of General
and Inorganic Chemistry, University of Parma, Parma, Italy.
3.5.3. Biphenyl-2-carboxaldehyde
A white solid, M.p. 69e74 ꢀC; 1H NMR (300 MHz, CDCl3, ppm):
¼ 10.01 (d, 4J(HeH) ¼ 0.9 Hz, 1H, CHO), 8.05 (dd, 3J(HeH) ¼ 7.5, 4J
d
Appendix A. supplementary data
(HeH) ¼ 1.2 Hz,1H, Ar), 7.7 (dt, 3J(HeH) ¼ 7.5, 4J(HeH) ¼ 1.2 Hz, 1H,
Ar), 7.55e7.39 (m, 7H, Ar) [46].
CCDC 783343 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via http://www.ccdc.cam.
ac.uk/deposit or deposit@ccdc.cam.ac.uk.
3.5.4. 1-Phenyl-naphthalene
M.p. 91e96 ꢀC; IR (KBr):
y
: 3056, 1592, 1493, 1395, 802, 779, 761,
703, 570. 1H NMR (300 MHz, CDCl3, ppm):
¼ 7.90e7.8 (m, 3H),
7.51e7.36 (m, 9H). 13C NMR (75 MHz, CDCl3, ppm):
d
d
¼ 140.9, 140.4,
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