Neutral trinuclear palladium(II) metallocycles with mixed phosphane/ pyridine-4-thiolato ligands and their catalytic tests in suzuki-miyaura

Article abstract of DOI:10.1002/ejic.200900895

Three neutral trinuclear palladium(II) complexes [Ph₃PPdCl(μ- 4-PyS)]₃ (1), [Cy₃PPdCl(μ-PySJ]₃ (2) and [(PhO)₃PPdCl(μ-4-PyS)]₃ (3) (4-PyS = pyridine-4-thiolate) were self-assembled from corresponding metal fragments [R₃PPdCl₂J₂ with lithium pyridine-4-thiolate (PySLi). The crystal structure reveals that: complex 1 possesses a triangular macrocyclic structure in which the distances of Pd(I)Pd(2), Pd(2)-Pd(3) and Pd(3)-Pd(l) are 7.764, 7.684 and 7.944 A, respectively, An equilibrium between trinuclear complex 1 and mononuclear complex (Ph₃P) ₂PdCl(4-PyS) (4) in solution through coordination and de-coordination of the PPh₃ ligand is confirmed by ₃₁P NMR spectroscopy, A comparative study on the Suzuki-Miyaura coupling reaction showed that: complexes 1 and. 2 are more active precatalysts than [R₃PPdCl ₂]₂ complexes without a. PyS group.

Full text of DOI:10.1002/ejic.200900895

FULL PAPER
DOI: 10.1002/ejic.200900895
Neutral Trinuclear Palladium(II) Metallocycles with Mixed Phosphane/
Pyridine-4-thiolato Ligands and Their Catalytic Tests in Suzuki–Miyaura
Coupling Reactions
Hui Wang,[a] Rui Zhong,[a] Xu-Qing Guo,[a] Xiao-Yan Feng,[a] and Xiu-Feng Hou*[a]
Keywords: Palladium / Metallocycles / Pyridinethiolate / Phosphanes / Catalytic tests / Suzuki–Miyaura cross-coupling
reactions
Three
[Ph3PPdCl(µ-4-PyS)]3 (1), [Cy3PPdCl(µ-4-PyS)]3 (2) and
[(PhO)3PPdCl(µ-4-PyS)]3 (3) (4-PyS pyridine-4-thiolate)
were self-assembled from corresponding metal fragments
[R3PPdCl2]2 with lithium pyridine-4-thiolate (PySLi). The
crystal structure reveals that complex 1 possesses a triangu-
lar macrocyclic structure in which the distances of Pd(1)···
Pd(2), Pd(2)···Pd(3) and Pd(3)···Pd(1) are 7.764, 7.684 and
neutral
trinuclear
palladium(II)
complexes
7.944 Å, respectively. An equilibrium between trinuclear
complex 1 and mononuclear complex (Ph3P)2PdCl(4-PyS) (4)
in solution through coordination and de-coordination of the
PPh3 ligand is confirmed by 31P NMR spectroscopy. A com-
parative study on the Suzuki–Miyaura coupling reaction
showed that complexes 1 and 2 are more active precatalysts
than [R3PPdCl2]2 complexes without a PyS group.
=
cycles with (R3P)PdCl at the corner and pyridine-4-thiolato
as the bridging ligand. We also find that these triangular
palladium complexes exhibit catalytic activity in the Su-
zuki–Miyaura cross-coupling reactions.
Introduction
In the past few years, there has been great interest in
supramolecular chemistry, since self-assembly of discrete
molecular architectures by using polytopic organic ligands
and transition metal complexes has proven a powerful tool
for constructing rings, polymers and networks. Some of
these compounds have potential applications in molecular
recognition, catalysis, optical materials, molecular magnet-
ism, semiconductors, etc.[1] In particular, square-planar pal-
ladium(II) complexes have been widely used to construct
numerous polygons, cages and catenanes with suitable lin-
ear, angular or flexible bridging ligands.[2] Within the wide
range of supramolecular architectures reported, the number
of molecular triangles is relatively small due to the lack of
suitable building blocks with proper turning angles.[3]
To the best of our knowledge, pyridinethiolato ligands
display a great versatility of coordination chemistry with
metal centers through their tautomeric and mesomeric
forms,[4] in which pyridine-4-thiolato is a potential bridge
ligand, since the sulfur atom and nitrogen atom can act as
terminal coordination donors. The less rigid structure and
proper turning angle both mean that the pyridine-4-thiolato
ligand is a suitable building block for the self-assembly of
triangular supramolecules.[5] In this paper, we report our
successful preparation of three neutral triangular macro-
Results and Discussion
Self-Assembly Reactions of 1, 2 and 3 with
4-Pyridinethiolate
The treatment of [Ph3PPdCl2]2 with 2 equiv. of lithium
pyridine-4-thiolate in thf resulted in the formation of
[Ph3PPdCl(µ-4-PyS)]3 (1) as orange crystals in good yield
(Scheme 1). The 31P NMR spectrum shows a unique signal
at δ = 32.35 ppm. Two doublet peaks (δ = 8.18, 6.95 ppm)
for the pyridine-4-thiolato ligand and three peaks (δ = 7.68,
7.44, 7.38 ppm) for PPh3 are displayed in the aromatic hy-
1
drogen region of the H NMR spectrum.
Single crystals of complex 1 suitable for X-ray diffraction
analysis were obtained by slow diffusion of hexane into a
concentrated solution of the complex in dichloromethane at
low temperature. As shown in Figure 1, the crystal structure
reveals that complex 1 possesses a triangular macrocyclic
structure in which the (PPh3)PdCl moiety holds the vertices,
and as a nonlinear bridging motif, the 4-PyS ligand is the
edge of the triangle through the coordination of the sulfur
atom and the nitrogen atom to two palladium atoms. The
distances of Pd(1)···Pd(2), Pd(2)···Pd(3) and Pd(3)···Pd(1)
are 7.764, 7.684 and 7.944 Å, respectively. The slightly dis-
torted square-planar geometry around each palladium cen-
ter comprises the Cl atom, the P atom of PPh3, and the S
[a] Department of Chemistry, Fudan University,
Han Dan Road 220, Shanghai 200433, P. R. China
Fax: +86-21-65641740
E-mail: xfhou@fudan.edu.cn
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.200900895.
174
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Eur. J. Inorg. Chem. 2010, 174–178

Neutral Trinuclear Palladium(II) Metallocycles
Scheme 1. Synthesis of complexes 1, 2 and 3.
and N atoms from different 4-PyS bridges, in which the two
coordinating bonds, Pd–P and Pd–N, are opposite. Three
Figure 1. Molecular structure of 1, ellipsoids at the 30% probability
Pd–S–C angles within the macrocycle (105.2, 106.8 and level. H atoms are omitted for clarity. Selected bond lengths [Å]
and angles [°]: Pd(1)–Cl(1) 2.311(3), Pd(1)–N(3) 2.118(8), Pd(1)–
111.7°, respectively) are smaller than the M–S–C angles in
S(1) 2.293(3), Pd(1)–P(1) 2.241(3), S(1)–C(1) 1.722(10); N(3)–
similar Rh and Ir complexes,[5e,5f] which means a bigger
Pd(1)–S(1) 90.6(2), N(3)–Pd(1)–Cl(1) 90.1(3), Cl(1)–Pd(1)–S(1)
176.48(11), N(3)–Pd(1)–P(1) 173.5(3), Pd(1)–S(1)–C(1) 106.8(4).
strain. In some cases, there exists an equilibrium between
trinuclear and tetranuclear cycles in solution because of
such a strain,[3g,3h,6] but the unique signal in the 31P NMR
A similar reaction of [(PhO)3PPdCl2]2 with lithium pyr-
spectrum proves that only the triangular structure exists in
idine-4-thiolate gave [(PhO)3PPdCl(µ-4-PyS)]3 (3) as an
orange solid. Although complexes 1 and 2 have a high solu-
this system. As shown in Figure 2, the molecular rectangles
stack along the a axis to form triangle channels due to the
bility in common organic solvents, complex 3 is insoluble
π–π interactions between the independent molecules.
in common solvents.
When [Cy3PPdCl2]2 was used in place of [Ph3PPdCl2]2,
the reaction solution changed from a brown mixture to a
clear yellow solution after about 3 h, and yellow acicular
Equilibrium between Trinuclear and Mononuclear
crystals of [Cy3PdCl(µ-4-PyS)]3 (2) formed by slow dif-
Complexes
fusion of hexane into a concentrated dichloromethane solu-
tion at low temperature. There is only one peak at δ =
When excess PPh3 was added to a solution of
45.52 ppm in the 31P NMR spectrum of complex 2. Two [Ph3PPdCl(µ-4-PyS)]3 (1) in CDCl3, the color of the mix-
doublet peaks (δ = 8.23, 7.12 ppm) for the pyridine-4-thiol- ture turned from orange to red immediately.
ato ligand at low field and multiple peaks (δ = 2.57, 1.96–
In the 31P NMR spectrum, the signal at δ = 32.35 ppm
1.64 ppm) for PCy3 at high field are appear in the 1H NMR for complex 1 disappeared, and two new peaks appeared.
spectrum.
One is for PPh3 at δ = –4.42 ppm, and the other (δ =
Figure 2. Crystal packing diagram of 1 viewed along the a axis.
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175

H. Wang, R. Zhong, X.-Q. Guo, X.-Y. Feng, X.-F. Hou
FULL PAPER
25.39 ppm) is assigned the mononuclear palladium complex ture repeatedly with Et2O (see Supporting Information).
(Ph3P)2PdCl(4-PyS) (4). However, all efforts to obtain pure Reasonably pure 4 may be isolated in the presence of excess
samples of 4 failed.
PPh3, but analytically pure samples could not be obtained.
In order to clarify our results, we tried to synthesize the A similar equilibrium was also found in PtII compounds by
mononuclear complex 4 by direct reaction of (Ph3P)2PdCl2 Krinsky.[7]
with 1 equiv. of lithium pyridine-4-thiolate. However, al-
though the product was isolated and recrystallized repeat-
edly, it still was a mixture of 4, 1 and PPh3 as confirmed by
Suzuki–Miyaura Cross-Coupling Reactions by Using
Palladium Complexes
31P NMR spectroscopy (δ = 25.39 ppm for 4, δ = 32.31 ppm
for 1, δ = –4.42 ppm for PPh3). It is likely that the complex
4 produced decomposed partially in solution to give PPh3,
and the residual Ph3PPdCl(4-PyS) moiety reassembled
through coordination of the nitrogen atom of the pyridine
ring with the palladium center to give trinuclear complex 1
(Scheme 2). The conversion of complex 4 to 1 can be ob-
served in their 31P NMR spectra by washing the solid mix-
It is now well established that palladium complexes con-
taining bulky phosphanes, which combine both a good σ-
donor strength and a π-accepting capacity, always have a
high catalytic activity in Suzuki–Miyaura cross-coupling re-
actions;[8] therefore we attempted to use our palladium(II)
metallocycles 1 or 2 in this well-known process.
The palladium complexes catalyze the cross-coupling re-
actions of aryl bromide and aryl boronic acid to afford the
desired biaryls in good yields at 100 °C by using toluene as
solvent (Table 1).
Complexes 1 and 2 bearing the PyS ligand are quite ef-
fective precatalysts in these reactions to give the corre-
sponding coupled products in better yields than [R3PPd-
Cl2]2, which indicates that no metal-poisoning occurs in the
presence of a sulfide group in the catalyst. Side products
derived from the reduction or homocoupling of the aryl
halides were not detected at all or were observed only in
trace amounts. The higher activities of the PCy3 complexes
(Entries 3 and 4) relative to the PPh3 complexes (Entries 1
Scheme 2. Equilibrium between complexes 4 and 1.
Table 1. Suzuki–Miyaura cross-coupling of aryl bromide with aryl boronic acid.[a]
[a] Reaction conditions: Aryl bromide (1 mmol), aryl boronic acid (1.5 mmol), K2CO3 as base (2 mmol), catalyst (0.1% Pd), toluene
1
(5 mL), 100 °C, 10 h. [b] Yields were determined by H NMR spectroscopy.
176
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Neutral Trinuclear Palladium(II) Metallocycles
δ = 162.19, 147.86, 125.35 (µ-4-PyS), 134.23, 130.97, 129.73, 128.31
(Ph) ppm. 31P NMR (202 MHz, CDCl3): δ = 32.35 (s) ppm. IR
and 2) can be attributed to the faster de-coordination of the
labile PCy3 ligand and facile formation of the Pd0 species.[9]
However, the close activities of complex 1 and 2 should
result from the presence of the PyS group. Without any at-
tempt to optimize the reaction conditions, these experi-
ments have demonstrated that the trinuclear palladium(II)
complexes 1 and 2 with mixed phosphane and pyridine-4-
thiolato ligands are effective precatalysts for the cross-cou-
pling of aryl bromides containing both electron-donating
and electron-withdrawing substituents.
(KBr disk): ν = 3056, 1591, 1480, 1435, 1110, 1060, 1024, 810, 730,
˜
692, 532, 511 cm–1.
Synthesis of [Cy3PPdCl(µ-4-PyS)]3 (2): A solution of nBuLi (1.6 ,
0.14 mL, 0.22 mmol) in hexane was added dropwise to a solution
of 4-mercaptopyridine (22 mg, 0.2 mmol) in thf (8 mL) at 0 °C. The
suspension was stirred at room temperature for another 1 h. Then
the solution was slowly added to a solution of [Cy3PPdCl2]2
(91 mg, 0.1 mmol) in thf (20 mL) at –78 °C. After it had been
stirred for 1 d, the solvent was removed under reduced pressure,
and the residue was extracted with CH2Cl2. The filtrate was con-
centrated to about 5 mL, and hexane was added to give 2 as yellow
solid. Yield: 81 mg, 76%. C69H111Cl3N3P3Pd3S3 (1597.38): calcd. C
51.88, H 7.00, N 2.63; found C 51.90, H 7.06, N 2.61. 1H NMR
(500 MHz, CDCl3): δ = 8.23 (d, JH,H = 6.8 Hz, 6 H, µ-4-PyS), 7.12
(d, JH,H = 5.6 Hz, 6 H, µ-4-PyS), 2.57 (m, 9 H, Cy), 1.96–1.64 (m,
90 H, Cy) ppm. 13C NMR (125 MHz, CDCl3): δ = 162.29, 147.68,
125.55 (µ-4-PyS), 34.33, 29.98, 27.51, 26.37 (Cy) ppm. 31P NMR
Conclusions
Three neutral trinuclear palladium(II) complexes with
mixed phosphane and pyridine-4-thiolato ligands are syn-
thesized. Single-crystal X-ray diffraction shows a triangular
structure in which the 4-PyS ligand plays a role as a nonlin-
ear bridging motif, and a unique signal in the 31P NMR
spectrum proves that only the triangle exists in this system.
With the help of 31P NMR spectroscopy, we found an equi-
librium between the trinuclear complex 1 and the mononu-
clear complex 4 in solution through coordination and de-
coordination of the PPh3 ligand. A preliminary study on
Suzuki–Miyaura couplings shows that the novel trinuclear
PdII complexes with a PyS bridge are more active precata-
lysts than [R3PPdCl2]2 complexes. Research in our labora-
tory is underway to extend the synthetic methodology to
other transition metals as well as to widen the scope of
these palladium complexes in catalysis.
(202 MHz, CDCl ): δ = 45.52 (s) ppm. IR (KBr disk): ν = 2932,
˜
3
2847, 1594, 1472, 1445, 1424, 1110, 1058, 1026, 809, 730, 516 cm–1.
Synthesis of [(PhO)3PPdCl(µ-4-PyS)]3 (3): A solution of nBuLi
(1.6 , 0.14 mL, 0.22 mmol) in hexane was added dropwise to a
solution of 4-mercaptopyridine (22 mg, 0.2 mmol) in thf (8 mL) at
0 °C. The suspension was stirred at room temperature for another
1 h. Then the solution was slowly added to a solution of [(PhO)3-
PPdCl2]2 (97 mg, 0.1 mmol) in thf (20 mL) at –78 °C. After it had
been stirred for 1 d, the solvent was removed under reduced pres-
sure, and the residue was extracted with CH2Cl2. The filtrate was
concentrated to about 5 mL, and hexane was added to give 3 as
orange solid. Yield: 64 mg, 56%. C69H57Cl3N3O9P3Pd3S3
(1686.95): calcd. C 49.13, H 3.41, N 2.49; found C 49.15, H 3.45,
N 2.50. 31P NMR (202 MHz, CDCl3): δ = 51.96 (s) ppm. IR (KBr
disk): ν = 3060, 1618, 1589, 1487, 1466, 1261, 1185, 1159, 1109,
˜
1024, 927, 807, 763, 729, 698, 457 cm–1.
Experimental Section
Reaction of (Ph3P)2PdCl2 with 4-LiSPy: A solution of nBuLi
(1.6 , 0.14 mL, 0.22 mmol) in hexane was added dropwise to a
solution of 4-mercaptopyridine (22 mg, 0.2 mmol) in thf (8 mL) at
0 °C. The suspension was stirred at room temperature for another
1 h. Then the solution was slowly added to a solution of (Ph3P)2-
PdCl2 (140 mg, 0.2 mmol) in thf (20 mL) at –78 °C. After it had
been stirred for 1 d, the solvent was removed under reduced pres-
sure, and the residue was extracted with CH2Cl2. The filtrate was
concentrated to about 5 mL, and hexane was added to give red
solid.
General: All reactions and manipulations were carried out under
nitrogen by using standard Schlenk techniques. Solvents were dried
and deoxygenated by an M. Braun Solvent Purification System
(4464) and collected just before use. [Ph3PPdCl2]2, [Cy3PPdCl2]2,
[(PhO)3PPdCl2]2 and (Ph3P)2PdCl2 were prepared according the lit-
erature methods.[10] 4-Mercaptopyridine, phenylboronic acid, p-tol-
ylboronic acid and 4-bromoanisole were used as purchased without
further purification. Elemental analyses were performed with an
Elementar III Vario EI Analyzer. Infrared spectra were recorded
with
a
Nicolet AVATAR-360IR spectrometer. 1H (500 MHz,
CDCl3, TMS), 13C (125 MHz, CDCl3, TMS) and 31P NMR spectra
(202 MHz, CDCl3, H3PO4) were obtained with a Bruker DMX-
500 spectrophotometer.
Crystal Structure Determination: Diffraction data of complex
1·3CH2Cl2 were measured at room temperature with a Bruker
SMART APEX CCD diffractometer with graphite-monochro-
mated Mo-Kα radiation (λ = 0.71073 Å). The structure was solved
by direct methods, and refined on F2 by full-matrix least-squares
methods (SHELXL).[11] The non-hydrogen atoms were refined an-
isotropically, and the hydrogen atoms were included but not re-
fined. Compound 1·3CH2Cl2 crystallized with highly disordered in-
terstitial solvent molecules. The diffuse electron density created by
the interstitial molecules in 1·3CH2Cl2 was analyzed by using the
program SQUEEZE in the PLATON software package.[12] CCDC-
746894 (for 1·3CH2Cl2) contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
Synthesis of [Ph3PPdCl(µ-4-PyS)]3 (1): A solution of nBuLi (1.6 ,
0.14 mL, 0.22 mmol) in hexane was added dropwise to a solution
of 4-mercaptopyridine (22 mg, 0.2 mmol) in thf (5 mL) at 0 °C. The
suspension was stirred at room temperature for another 1 h. Then
the solution was slowly added to a solution of [Ph3PPdCl2]2 (88 mg,
0.1 mmol) in thf (20 mL) at –78 °C. After it had been stirred for
1 d, the solvent was removed under reduced pressure, and the resi-
due was extracted with CH2Cl2. The filtrate was concentrated to
about 5 mL, and hexane was added to give 1 as orange solid. Yield:
84 mg, 82%. C69H57Cl3N3P3Pd3S3 (1542.95): calcd. C 53.71, H
1
3.72, N 2.72; found C 53.66, H 3.75, N 2.70. H NMR (500 MHz,
CDCl3): δ = 8.18 (d, JH,H = 6.5 Hz, 6 H, µ-4-PyS), 6.95 (d, JH,H
=
5.7 Hz, 6 H, µ-4-PyS), 7.70–7.66 (m, 18 H, Ph), 7.45–7.44 (m, 9 H,
Suzuki–Miyaura Cross-Coupling Reactions: In a typical run, a mix-
ture of 4-bromoanisole (1 mmol), arylboronic acid (1.5 mmol),
Ph), 7.43–7.36 (m, 18 H, Ph) ppm. 13C NMR (125 MHz, CDCl3):
Eur. J. Inorg. Chem. 2010, 174–178
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H. Wang, R. Zhong, X.-Q. Guo, X.-Y. Feng, X.-F. Hou
FULL PAPER
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Supporting Information (see also the footnote on the first page of
this article): Crystal data of complex 1·3CH2Cl2, NMR spectra
1
(1H, 13C, and 31P) of all new complexes, and H NMR spectra of
Suzuki–Miyaura cross-coupling reactions.
Acknowledgments
Financial support by the National Science Foundation of China
(Grant No. 20871032, 20971026) and the Shanghai Leading Aca-
demic Discipline Project (Project Number B108) is gratefully ac-
knowledged. We thank Professor Jie Wu for helpful discussions.
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Received: September 9, 2009
Published Online: November 24, 2009
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