Structure and heterogeneous catalytic activity of a coordination polymer containing Cu(NO3)2 and Cu(H2O) 22+ units bridged alternatively by btp ligands (btp=2,6-bis(N′-1,2,4-triazolyl)pyridine)

Article abstract of DOI:10.1016/j.molstruc.2005.05.006

The reaction of Cu(NO₃)₂ containing NH ₄PF₆ with btp ligands produced a new polymeric compound 1 containing Cu(H2O)22+ and Cu(NO₃)₂ units alternatively bridged by btp ligands with H-bonds between copper-bonded water and nitrate oxygen atoms. Crystal Data: M=1465.97, space group P2/n, a=11.6300(3) ?, b=12.8000(4) ?, c=19.2960(6) ?, β=98.6200(19)°, V=2840.03(15) ?³, Z=2, μ=0.926 mm^-1, Dc=1.714 Mg/m³, R=0.0629, wR=0.1614. The polymeric compound 1 has shown the heterogeneous catalytic activity for the ring opening of epoxides under mild conditions. This catalyst system appears to be an efficient, mild, and easily recyclable method for the alcoholysis of epoxides. In addition, the heterogeneous catalyst 1 has, surprisingly, shown even better catalytic activity than copper salt system in homogeneous condition.

Full text of DOI:10.1016/j.molstruc.2005.05.006

Journal of Molecular Structure 751 (2005) 22–28
www.elsevier.com/locate/molstruc
Structure and heterogeneous catalytic activity of a coordination polymer
2C
containing Cu(NO3)2 and CuðH2OÞ units bridged alternatively by btp
ligands (btpZ2,6-bis(N02-1,2,4-triazolyl)pyridine)
Sung Jin Honga, Jin Soo Seoa, Ji Young Ryua, Jung Hwan Leea, Cheal Kima, ,1
,
*
Sung-Jin Kimb, Youngmee Kimb, ,2, Alan J. Loughc
*
aDepartment of Fine Chemistry, Seoul National University of Technology, Seoul 139-743, South Korea
bDivision of Nano Sciences, Ewha Womans University, Seoul 120-750, South Korea
cDepartment of Chemistry, University Toronto, Toronto, Ont., Canada M5S 3H6
Received 24 March 2005; revised 3 May 2005; accepted 3 May 2005
Available online 13 June 2005
Abstract
2C
The reaction of Cu(NO3)2 containing NH4PF6 with btp ligands produced a new polymeric compound 1 containing CuðH2OÞ2 and
Cu(NO3)2 units alternatively bridged by btp ligands with H-bonds between copper-bonded water and nitrate oxygen atoms. Crystal Data:
3
˚
˚
˚
˚
MZ1465.97, space group P2/n, aZ11.6300(3) A, bZ12.8000(4) A, cZ19.2960(6) A, bZ98.6200(19)8, VZ2840.03(15) A , ZZ2, mZ
0.926 mmK1, DcZ1.714 Mg/m3, RZ0.0629, wRZ0.1614. The polymeric compound 1 has shown the heterogeneous catalytic activity for
the ring opening of epoxides under mild conditions. This catalyst system appears to be an efficient, mild, and easily recyclable method for the
alcoholysis of epoxides. In addition, the heterogeneous catalyst 1 has, surprisingly, shown even better catalytic activity than copper salt
system in homogeneous condition.
q 2005 Elsevier B.V. All rights reserved.
Keywords: Polymeric compound; Copper complex; Crystal structure; Catalyst; Ring opening of epoxide
1. Introduction
1,2-bis(4-pyridyl)ethyne [9], 1,2-bis(4-pyridyl)ethane [10],
and 1,3-bis(4-pyridyl)propane [11] have been utilized, the
angular bifunctional ligands are far less studied [12].
Self-assembly of organic ligands and inorganic metal
ions is one of the most efficient and widely used approaches
for the construction of supramolecular architectures [1].
Owing to their potential as new functional solid materials
such as gas or chemical absorption [2], ion-exchange [3],
magnetism [4], host–guest chemistry [5], and catalysis [6],
interest in self-assembled coordination polymers has grown
rapidly. In this field, the coordination chemistry of bidentate
rigid or flexible organodiamine ligands has been the main
interest. While several types of those organodiamine ligands
such as 4,40-bipyridine [7], 1,2-bis(4-pyridyl)ethene [8],
Therefore, in our attempt to investigate the design and
control of the self-assembly of coordination polymers with
the angular bridging ligands, we initiated a synthetic
program for the construction of various supramolecular
complexes with interesting extended frameworks based on
the angular btp (2,6-bis(N0-1,2,4-triazolyl)pyridine) ligand
[13]. We have previously reported that Cu(II) salts with btp
ligands produced coordination polymers as well as a
monomeric molecule [6d,e]. In all btp-bridged Cu-contain-
ing coordination polymers, the geometry of Cu(II) ion has
D4h symmetry, and both Jahn–Teller effect and counter
anion effect are very important roles for the construction of
coordination crystal structures. In addition, the polymeric
Cu(II) compounds showed, surprisingly, an unexpected
heterogeneous catalytic reactivity and recyclability for
alcoholysis of epoxides at ambient temperature. These
results have prompted us to design new polymeric
compounds as a potential heterogeneous catalyst. Therefore,
Corresponding authors. 1Tel.:C82 2 970 6693; fax:C82 2 973 9149;
*
2Tel.: C82 232 773589; fax: C82 232 772384.
E-mail addresses: chealkim@snut.ac.kr (C. Kim), ymeekim@ewha.ac.
kr (Y. Kim).
0022-2860/$ - see front matter q 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molstruc.2005.05.006

S.J. Hong et al. / Journal of Molecular Structure 751 (2005) 22–28
23
we have synthesized and characterized a new polymeric
2.4. Catalytic activity of the polymeric compound
1 and copper salt
compound 1 by the reaction of the btp ligand and copper
nitrate with NH4PF6, and we have examined the reactivity
of the polymeric compound 1 as a potential heterogeneous
catalyst for the ring opening of epoxides under mild
conditions.
Catalytic reaction conditions: epoxides (0.05 mmol)
were dissolved in methanol (1 mL), and the polymeric
compound (1 mg/FW of 1Z0.68!10K4 mmol), which was
ground well into appropriate sizes for high surface area but
not too small for convenient filtration, was added and
shaken at room temperature (450 rpm). Reaction conversion
was monitored by GC/GC-Mass analysis of 20 mL aliquots
withdrawn periodically from the reaction mixture. All
reactions were run at least three times and the average
conversion yields are presented. Conversion yield was
based on the consumption of the starting epoxide. Reaction
conditions for the homogeneous copper salt were the same
as above described except that 2!10K3 mmol of copper salt
was used instead of the polymeric compound 1.
Herein, we report crystal structure of another new
Cu-containing polymeric compound 1 obtained by the
reaction of Cu(NO3)2 containing NH4PF6 with btp ligands,
and a systematic study of the heterogeneous catalytic ring
opening of epoxides by the polymeric compound 1.
2. Experimental
2.1. Materials
2.5. Crystallography
The btp (2,6-bis(N0-1,2,4-triazolyl)pyridine) was syn-
thesized by previous method [13]. 2,6-Dibromopyridine,
potassium triazole, methanol and diglyme were purchased
from Aldrich and used as received. Epoxides (cyclohexene
oxide, cyclopentene oxide, styrene oxide, cis-2,3-epoxybu-
tane, trans-2,3-epoxybutane) and their products trans-diol
mono-ethers were also obtained from Aldrich and used
without further purification.
Crystal Data: C36H36Cu2F12N30O10P2, MZ1465.97,
monoclinic, TZ150(1) K, aZ11.6300(3) A, bZ
˚
˚
12.8000(4) A,
˚
cZ19.2960(6) A,
bZ98.6200(19)8,
3
˚
VZ2840.03(15) A , space group P2/n, ZZ2, m(Mo Ka)Z
0.926 mmK1, DcZ1.714 Mg/m3, F(000)Z1476, 20950
reflections measured, 6483 unique (RintZ0.0547) which
were used in all calculations, final RZ0.0629 (RwZ0.1614)
with reflections having intensities greater than 2q,
GOF(F2)Z0.993. The diffraction data were collected on a
Nonius Kappa-CCD diffractometer using Mo Ka (lZ
2.2. Instrumentation
˚
0.71073 A) [14]. The crystal was mounted on a glass fiber
Elemental analysis for carbon, nitrogen, and hydrogen
was carried out by using an EA1108 (Carlo Erba Instrument,
Italy) in the Organic Chemistry Research Center of Sogang
University, Korea. Product analyses for the ring opening of
epoxides were performed on either a Hewlett-Packard 5890
II Plus gas chromatograph interfaced with Hewlett-Packard
Model 5989B mass spectrometer or a Donam Systems 6200
gas chromatograph equipped with a FID detector using
30-m capillary column (Hewlett-Packard, HP-1, HP-5, and
Ultra 2). PXRD data were obtained using a Rigaku X-ray
under epoxy resin. The CCD data were integrated and scaled
using the DENZO-SMN software package [15], and the
structures were solved by direct method and refined by using
SHEXTL/PC V5.1 [16]. During the refinement it was noticed
that one of the PFK6 anions was highly disordered over several
sites and attempts to model the anion were unsuccessful. In
addition, what appeared to be a water molecule was also
grossly disordered. Ultimately, the contributions from these
species were removed using the SQUEEZE option in
PLATON [17]. This procedure did not affect the geometry
of therestof thestructure, butdid improvetheprecision ofthe
geometric parameters. The contributions of the removed
species are included in the empirical formula. All hydrogen
atoms were placed in thecalculated positions. The crystal and
experimental data are given in Table 1. The bond distances
and angles are listed in Table 2. The molecular structure was
drawn by the Ortep-3 for Windows program [18].
˚
diffractometer with Cu Ka radiation (lZ1.5418 A).
2.3. Synthesis of a polymeric compound [Cu(H2O)2–(btp)2–
Cu(NO3)2](PF6)2 1
57.4 mg (0.3 mmol) of Cu(NO3)2 and 97.8 mg
(0.6 mmol) of NH4PF6 were dissolved in 20 mL water and
carefully layered by 20 mL methanol solution of btp ligand
(128.5 mg, 0.6 mmol). Suitable crystals of the compound 1
for X-ray analysis were obtained in a few days. Anal. Calcd.
for C36H36Cu2F12N30O10P2 (1465.97): C, 29.49; H, 2.48; N,
28.67. Found: C, 29.75; H, 2.30; N, 28.58%. IR (KBr):
n(cmK1)Z3446(brs), 3127(brm), 1615(m), 1527(m),
1481(s), 1384(m), 1282(m), 1218(m), 1141(m), 1223(w),
1070(m), 980(m), 842(s), 799(m), 671(m), 557(m), 468(w).
3. Results and discussion
3.1. Structure description
The btp ligands have acted as bridging ligands with
different copper salts to form different polymeric

24
S.J. Hong et al. / Journal of Molecular Structure 751 (2005) 22–28
Table 1
ligands produced a new compound containing Cu(NO3)2
and units bridged alternatively by btp ligands.
Crystal and experimental data for [Cu(H2O)2–(btp)2–Cu(NO3)2](PF6)2
Asymmetric unit of the new compound 1 without PFK6
anions is shown in Fig. 1(a). The complete compound
structure is generated by the symmetry operations (KxC1,
Ky, KzC1), (Kx, KyC1, KzC1) and (KxC1, KyC1,
KzC1) as shown in Fig. 2(b). Two btp ligands bridge
Cu(NO3)2 units and CuðH2OÞ22C units alternatively to form
an one-dimensional coordination polymer with H-bonds
between copper-bonded water and nitrate oxygen atoms
(O1(water)–H/O3(nitrate) and O1(water–H/O4(nitrate)
Empirical formula
C36H36Cu2F12N30O10P2
Formula weight
Temperature
1465.97
150(1) K
˚
0.71073 A
Wavelength
Crystal system
Space group
Monoclinic
P2/n
˚
Unit cell dimensions
aZ11.6300(3) A aZ908
˚
bZ12.8000(4) A bZ98.620(19)8
˚
cZ19.2960(6) A gZ908
3
˚
2840.03(15) A
Volume
K
Z
2
˚
distances of 2.886(1) and 3.126(2) A, respectively). PF6
anions connect each one-dimensional polymer to form a
two-dimensional compound with noncovalent interchain C–
Density (calculated)
Absorption coefficient
F(000)
1.714 Mg/m3
0.926 mmK1
1476
0.30!0.12!0.08 mm3
2.72–27.478
˚
H/F interaction (C11–H11/F1 distance of 2.430(1) A)
Crystal size
q range
and intrachain C–H/F interactions (C8–H8/F2 and C1–
Index ranges (h, k, l)
Reflections collected
Independent reflections
Completeness to thetaZ27.478
Absorption correction
Max. and min. transmission
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R, wR indices [IO2s(I)]
R, wR indices (all data)
Extinction coefficient
Largest diff. peak and hole
K15/15, K15/16, K24/25
20950
˚
H1/F2 distances of 2.730(1) and 2.66(1) A, respectively)
(Fig. 2). The Cu–N(btp) distances range from 2.007(3) to
6483 [R(int)Z0.0547]
99.5%
˚
2.041(3) A. The Cu1–O1(water) distance is 2.360(3), and
˚
the Cu2–O(nitrate) distance is 2.399(3) A. The O1(water)–
Semi-empirical from equivalents
0.975 and 0.930
Full-matrix least-squares on F2
6483/2/386
Cu1–O1(water) and O2(nitrate)–Cu2–O2(nitrate) angles are
1808 (Table 2).
The coordination of Cu(II) ion in the new compound 1
has also D4h symmetry as previously reported Cu-contain-
ing polymeric compounds. The Cu–N(btp) distances of all
0.993
0.0629, 0.1614
0.1094, 0.1805
0.0055(8)
˚
these Cu-containing polymeric compounds are about 2.0 A
K3
˚
0.631 and K0.782 eA
˚
(1.978(3)–2.061(3) A for nitrate anions, 2.021(2) A for
˚
˚
perchlorate anions, 1.990(4) A for sulfate anions, and
˚
2.007(3)–2.041(3) A for the new compound 1 with nitrate
compounds. With nitrate anions, btp-bridged tetranuclear
Cu(II) units were weakly connected by nitrate ions to form a
polymeric compound [6d], while double zigzag chains and
single zigzag chains were formed with perchlorate anions
and sulfate anions, respectively [6e]. The btp ligand has also
acted as a monodentate ligand to form a discrete molecule
with Cu(O2CCH3)2 [6d]. To see the anion effect for
construction of polymeric compounds, we added PFK6
anions to the Cu(NO3)2 solution with btp ligands.
The reaction of Cu(NO3)2 containing NH4PF6 with btp
and PFK6 anions). The distances between Cu(II) ion and axial
˚
ligands are enlongated (2.359(2)–2.482(2) A for nitrate
˚
anions, 2.398(17) A for perchlorate anions, 2.469(16) A for
˚
˚
sulfate anions, and 2.360(3)–2.399(3) A for the new
compound 1) (Table 3). These results indicate that all of
the Cu-containing polymeric compounds show D4h sym-
metry due to Jahn–Teller effect of the electronic configur-
ation of Cu(II). The Cu/Cu distance of this new compound
˚
is 8.647(1) A, that is the shortest distance in these
Cu-containing polymeric compound series (Table 3). This
is because of H-bonds between copper-bonded water and
nitrate oxygen atoms.
Table 2
˚
Bond distances (A) and angles (8) for [Cu(H2O)2–(btp)2–Cu(NO3)2](PF6)2
In summary, Cu(NO3)2 and btp ligands produced a
different polymeric structure by adding PFK6 anions. The
new polymeric compound 1 contains CuðH2OÞ22Cand
Cu(NO3)2 units alternatively bridged by btp ligands with
H-bonds between copper-bonded water and nitrate oxygen
atoms. Our study of these Cu-containing btp-bridged
polymeric compounds confirms that both Jahn–Teller effect
and anion effect are very important roles for construction of
polymeric structures.
Bond lengths
Cu(1)–N(1)
Cu(1)–O(1)
Cu(2)–N(7)
2.018(3)
2.360(3)
2.008(4)
Cu(1)–N(14)
Cu(2)–N(8)
Cu(2)–O(2)
2.041(3)
2.007(3)
2.399(3)
Bond angles
N(1)–Cu(1)–N(1)#1
180.0
N(1)–Cu(1)–N(14)
N(14)–Cu(1)–N(14)#1
N(14)–Cu(1)–O(1)#1
N(14)–Cu(1)–O(1)
N(8)#2–Cu(2)–N(8)
N(8)–Cu(2)–N(7)
89.3(11)
180.0
N(1)#1–Cu(1)–N(14) 90.7(11)
N(1)–Cu(1)–O(1)#1
N(1)–Cu(1)–O(1)
90.7(11)
89.3(11)
180.0
88.9(11)
91.1(11)
180.0
O(1)#1–Cu(1)–O(1)
N(8)#2–Cu(2)–N(7)
N(7)–Cu(2)–N(7)#2
N(8)–Cu(2)–O(2)#2
N(7)–Cu(2)–O(2)
87.8(14)
180.0
92.2(14)
91.6(12)
87.1(13)
180.0
N(8)–Cu(2)–O(2)
3.2. Heterogeneous catalytic activity of the new compound 1
88.4(12)
92.9(13)
N(7)–Cu(2)–O(2)#2
O(2)#2–Cu(2)–O(2)
Though a huge number of the polymeric compounds
have been developed over the past 10 years, their
application as heterogeneous catalysts is very rare [6].
Symmetry transformations used to generate equivalent atoms: #1 KxC
1,Ky,KzC1; #2 Kx,KyC1,KzC1; #3 KxC1,KyC1,KzC1.

S.J. Hong et al. / Journal of Molecular Structure 751 (2005) 22–28
25
Fig. 1. (a) Asymmetric unit for the polymeric compound 1 with labeling atoms. (b) One-dimensional structure with strong H-bonds between copper-bonded
water and nitrate oxygen atoms. PFK6 anions were omitted for clarity.
Therefore, the use of the polymeric compounds as catalysts
for various organic reactions is important and meaningful.
We have previously reported that two Cu-containing
polymeric compounds were found to be good heterogeneous
catalysts [6d,e] that offers the practical advantages of
simplifying the separation and isolation of products, and of
the potential for catalyst recycling [19]. These results have
prompted us to design new polymeric compounds as a
potential heterogeneous catalyst. Therefore, we have
synthesized and characterized the polymeric compound 1
by the reaction of the btp ligand and copper nitrate with
NH4PF6 and we have examined the reactivity of the
polymeric compound 1 as a potential heterogeneous catalyst
for the ring opening of epoxides under mild conditions.
The reaction was complete in 4 days when a mixture of the
catalyst and cyclohexene oxide in methanol was shaken at
room temperature (Eq. (1) and see entry 1 of the third
column in Table 4), while a control reaction carried out
in absence of the catalyst 1 showed trace amounts of
the conversion of the oxide to the product in the same time
period. Importantly, the catalyst 1 shows the best efficiency
among the polymeric compounds that we have previously
reported.
OMe
catalyst 1
+
MeOH
O
OH
(1)
Then, we have performed another control reaction
before further reactivity study with other substrates,
because in the catalysis process of the catalyst 1 the
leached copper species might catalyze efficiently the ring-
opening reaction instead of the catalyst 1. To test for this
possibility we have filtered the catalyst after the ring-
opening reaction of cyclohexene oxide and allowed the
filtered catalyst and the filtrate to react with another
aliquot of cyclohexene oxide, respectively, as shown in

26
S.J. Hong et al. / Journal of Molecular Structure 751 (2005) 22–28
carried out efficiently, and the results are given in Table 4
(see the third column). Cyclopentene oxide was completely
converted by 1. Moreover, this novel catalyst 1 was active
to acyclic epoxides, as cis- and trans-2-butene oxides were
ring-opened to the corresponding products in 10 and
30 days, respectively. All products were found to have a
trans conformation by NMR, GC and GC/MS analysis,
comparing to authentic samples.
More importantly, the catalyst 1 could be easily
recovered by a simple filtration and used repeatedly with
about 5–10% decrease of the original catalytic activity.
These results suggest that the polymeric compound 1 could
also be used as a useful heterogeneous catalyst. Decrease of
the catalytic activity is presumably due to leaching of
copper metal during the ring-opening reaction. On the other
hand, the powder X-ray diffraction (XRD) pattern of the
filtered catalyst after the reaction revealed the same pattern
as the original catalyst, suggesting that the original structure
of the filtered catalyst has been kept during the reaction (see
Fig. 3). Based on these results, we have concluded that the
heterogeneous catalyst 1 could be recycled multiple times
without a significant loss of activity.
Fig. 2. Two-dimensional structure with noncovalent C–H/F interactions.
In the regioselectivity study, styrene oxide was
converted to 2-methoxy-2-phenyl ethanol within 1.2 days.
That is, the methoxy group was, exclusively, incorporated
at the benzylic position (a-carbon) instead of the less
hindered b-carbon center to generate primary alcohol,
showing no steric preference for the methanol nucleophile.
In addition, the reactions with 1 have shown the same
product patterns for styrene oxide (primary alcohol only) as
the previous study [6d,e]. We have observed that the ring-
opening reaction with the filtered catalyst proceeded at
90–95% of the original rate, while the filtrate showed about
5–10% conversion within the same time interval. This
result strongly suggests that the dominant reactive species
is the heterogeneous catalyst 1, not the other species. The
alcoholysis of other epoxides by the compound 1 was also
Table 3
Comparison of bond distances of Cu(II)-containing polymeric compounds
Cu–N(btp)
Cu-axial ligand
Cu/Cu
a
NOK3
˚
1.978(3)–2.061(3) A
˚
Cu–O(monodentate nitrate) 2.359(2), 2.275(2) A
˚
9.659(7), 10.014(7) A
˚
Cu–O(bridging nitrate) 2.482(2), 2.420(2) A
b
ClOK4
SO24K
2.398(17) A
˚
2.469(16) A
˚
2.021(2) A
˚
1.990(4) A
˚
2.007(3)–2.041(3) A
˚
˚
9.871(1) A
˚
9.341(9) A
b
c
NOK3 and PFK6
8.647(1) A
˚
Cu–O(water) 2.360(3) A
˚
˚
Cu–O(nitrate) 2.399(3) A
a
From Ref. [6d].
b
c
From Ref. [6e].
This work.
Table 4
Ring opening of epoxides by methanol in the presence of the polymeric compound 1 and the corresponding copper salt at room temperature
Entry
Substrate
1 (1 mg) (time/days)
Cu(NO3)2C2NH4PF6 (2 mM) (time/days)
1
2
3
4
5
Cyclohexene oxide
Cyclopentene oxide
cis-2,3-Epoxybutane
trans-2,3-Epoxybutane
Styrene oxide
4
15
30
100
10
30
25
50
1.2 (primary alcohol only)
5 (primary alcohol only)
All epoxides were completely converted to the corresponding products. See Section 2 for the detailed reaction conditions. The concentrations of the complexes
used in this study were 0.68 mM for 1 and 2 mM for Cu(NO3)2, respectively. Control reactions carried out in absence of the catalyst 1 and copper salt showed
trace amounts of conversion of the oxide to the product in the same time period.

S.J. Hong et al. / Journal of Molecular Structure 751 (2005) 22–28
27
This observation is very significant, since it encourages us to
construct new polymeric compounds that could be
efficiently used as heterogeneous catalysts friendly to the
environment.
After
4. Supplementary materials
CCDC-266142 for 1 contains the supplementary
crystallographic data for this paper. These data can be
obtained free of charge at www.ccdc.cam.ac.uk/conts/
retrieving.html [or from the Cambridge Crystallographic
Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK;
fax: (internet) C44-1223/336-033; E-mail: deposit@ccdc.
cam.ac.uk].
Before
10
20
30
40
50
60
2 Theta
Fig. 3. PXRD patterns of the compound 1 after the catalytic reaction (upper)
and before the reaction (down).
Acknowledgements
the previously reported polymeric compounds [6d,e],
indicating that all the catalysts carry out the ring opening
of epoxide possibly by the same reaction mechanism. The
possible ring-opening mechanism with styrene oxide as a
substrate can be proposed as shown in Eq. (2). The more
substituted carbon in the intermediate adduct generated
from the substitution of the labile water in the catalyst 1 by
the oxide might have a significant cationic character which
can be stabilized by the phenyl group through conjugation.
Then, the nucleophile methanol would attack the
more cationic carbon to produce trans-2-methoxy-2-
phenylethanol.
Financial support from the Korean Science and Engin-
eering Foundation (ABRL R14-2003-014-01-001-0 and
R01-2005-000-10490-0(2005)) and the Korea Research
Foundation
acknowledged.
(2002-070-C00053)
is
gratefully
References
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δ-
δ+
Ph
O
OH2
+
(btp)4Cu
H2O
MeOH
OCH3
Ph
(2)
(btp)4Cu
H2O
(btp)4Cu
H2O
+
O
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(c) B. Moulton, M.J. Zaworotko, Chem. Rev. 101 (2001) 1629;
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In general, since heterogeneous systems for ring opening
were reported to show lower reactivity than the correspond-
ing homogeneous systems [20], we compared the hetero-
geneous and the homogeneous catalytic reactivity with the
polymeric compound 1 (1 mg: 0.68 mM) and the corre-
sponding copper salt system, Cu(NO3)2/2NH4PF6 (2 mM),
for the ring opening of epoxides in methanol at room
temperature. The results from the ring opening of epoxides
with the insoluble polymeric compound 1 and the soluble
copper salt system are also shown in Table 4 (see the third
and fourth columns). As it can be seen, the conversion rates
obtained with the polymeric compound 1 were much faster
than those of the corresponding copper salt system (9–12
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