Immobilization of Carbonylcobalt Catalyst by Poly(4-vinylpyridine) (P4VP) through N→Co Coordination Bonds: The Promotional Effect of Pyridine and the Reusability of Polymer Catalyst

Article abstract of DOI:10.1002/asia.201601100

A carbonylcobalt catalyst, immobilized by poly(4-vinylpyridine) (P4VP) through N→Co coordination bonds, has been prepared by solvothermal method. It has been revealed that the pyridine fragments in the polymer catalyst act not only as promoters to improve the catalytic performance of the carbonylcobalt catalyst for alkoxycarbonylation of ethylene oxide to methyl 3-hydroxypropanoate but also as stabilizers to enhance the reusability of the polymer catalyst. Furthermore, the polymer catalyst could be easily separated by filtration and reused with only a slight loss of catalytic efficiency.

Full text of DOI:10.1002/asia.201601100

CHEMISTRY
AN ASIAN JOURNAL
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Accepted Article
Title: Immobilization of carbonylcobalt catalyst by poly (4-vinylpyridine)(P4VP)
through N→Co coordination bonds:the promotional effect of pyridine and the
reusability of polymer catalyst
Authors: Yubing Liu; Yining Wang; Haimeng Lu; Shuang Liang; Bolian Xu; Yining
Fan
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Immobilization of carbonylcobalt catalyst by poly (4-vinylpyridine)
(P4VP) through N→Co coordination bonds: the promotional effect
of pyridine and the reusability of polymer catalyst
Yu-Bing Liu,[a, b] Yi-Ning Wang,[a, b] Hai-Meng Lu,[b] Shuang Liang,[a] Bo-Lian Xu,[a, b] and Yi-Ning Fan*[a, b]
Abstract: A carbonylcobalt catalyst has been immobilized by poly
(4-vinylpyridine) (P4VP) through N→ Co coordination bonds has
been prepared by solvothermal method. It has been revealed that
the pyridine fragments in the polymer catalyst act not only as
promoters to improve the catalytic performance of carbonylcobalt
catalyst for alkoxy-carbonylation of ethylene oxide to methyl 3-
hydroxypropanoate but also as stabilizers to enhance the reusability
of polymer catalyst.
However, the ion pairs in the ionic compound [ILs]+[Co(CO)4]-
are combined by a relatively weak ionic bond, which probably
makes the ions leach out especially in contact with water or
some other strong polar solvents. Obviously, it is preferable that
the carbonylcobalt catalysts are immobilized in solid polymer
materials containing ligands through
a
relatively strong
coordination bond because the polymer catalysts are easy to
separate, and the catalysts stability are potentially enhanced by
confinement and coordination effects.[6]
Herein, we report the synthesis, characterization and
catalytic performance of a recyclable poly (4-vinylpyridine) -
carbonylcobalt polymer catalyst.[7] The catalytic activity,
selectivity and reusability of the polymer catalysts are
satisfactory, and their structures have been well-defined by
using various physico-chemical methods.
It is well known that carbonylcobalt coordination compounds
like Co2(CO)8 and Na[Co(CO)4] are the key homogeneous
catalysts and have been widely used in the alkoxy-carbonylation
of epoxides as well as in the hydroformylation of olefins.[1]
Recently, carbonylcobalt-catalyzed alkoxy-carbonylation of
ethylene oxide (EO) to methyl 3-hydroxypropanoate (3-MHP)
and subsequent hydrogenation of 3-MHP to 1,3-propanediol
(1,3-PDO) have attracted much attention, because this route is
an atom economic and environmentally benign process for
production of 1,3-PDO intermediate to synthesize the advanced
polypropylene terephthalate (PTT) fibers:[2]
The carbonylcobalt polymer catalyst studied in this work was
synthesized by solvothermal method, in which the synthesis
procedures were described in detail in the supporting
information (SI) section. Commercially available poly (4-
vinylpyridine) (P4VP) and Co2(CO)8 were used as starting
materials and reacted in a mixed solvent THF/CH3OH (1:3 V/V)
at 75 oC under 3 MPa CO atmosphere for 24 h. From Figure S1
(a,b), one can see that the solvothermal treatment results in
swelling of P4VP polymer materials. Moreover, the swelling
degree of Co2(CO)8 loaded sample is higher than that of bare
P4VP sample (Figure S1 b,c), suggesting that Co2(CO)8 reacts
with P4VP in the solvothermal system. As determined by an
inductively coupled plasma optical emission spectroscopy (ICP-
OES) method, the as-prepared catalyst contained 16.1 wt% Co,
8.1 wt% N, i.e., n(Co)/n(N) = 1/2 (molar ratio). The energy
diffusion spectroscopy (EDS) image displayed a homogeneous
distribution of Co and N in the solid polymer materials (Figure
S2), and the X-ray diffraction (XRD) pattern indicated that the
polymer materials were in an amorphous state (Figure S3).
The gas chromatography-mass spectrometer (GC-MS)
analysis results indicated that methyl 3-hydroxypropanoate (3-
MHP) was a main product of EO alkoxy-carbonylation reaction
catalyzed by carbonylcobalt. Besides, ethylene glycol (EG), 2-
methoxyethanol (EM) and ethylene glycol dimethylether
(EGDME) were also formed as the by-products in the reaction
(S1). Table 1 listed the EO conversion and product selectivity of
Co2(CO)8 catalyst in a homogeneous reaction system with or
without organic compound as promoters under the same
reaction conditions. For Co2(CO)8 catalyst without any promoter,
EO conversion was 87.5 % with 3-MHP selectivity of 37.2 %. In
contrast, pyridine itself didn’t show any catalytic activity for EO
alkoxy-carbonylation to form 3-MHP. Interestingly, Co2(CO)8-
pyridine gives both higher EO conversion and higher 3-MHP
selectivity, suggesting that for the alkoxy-carbonylation of EO
catalyzed by Co2(CO)8-pyridine, Co2(CO)8 acts as a main
EO + CH3OH + CO = HO-CH2CH2COOCH3 (3-MHP)
3-MHP + H2 = CH3OH + HO-CH2CH2CH2-OH (1,3-PDO)
In fact, the carbonylcobalt catalysts with nitrogen heterocyclic
compounds as promoters have been found to be the effective
catalysts for alkoxy-carbonylation of EO in the homogeneous
catalytic reaction system,[3,4] however, it is very difficult to
separate the catalysts from mixture products and to reuse them.
The most challenging problem in production of 1,3-PDO from
EO is to explore a stable and reusable carbonylcobalt catalyst
for alkoxy-carbonylation of EO. So far, great efforts have been
made in preparation of reusable catalysts and in studying their
catalytic properties for the alkoxy-carbonylation of epoxides.[4a, 5]
As previously reported, the organometallic ionic liquids
[ILs]+[Co(CO)4]- exhibited excellent catalytic performances and
considerable reusability for the alkoxy-carbonylation of EO.
[a]
Y.-B. Liu, Y.-N. Wang, S. Liang, Dr. B.-L. Xu, Prof. Y.-N. Fan
Key Laboratory of Mesoscopic Chemistry of MOE
School of Chemistry and Chemical Engineering
Nanjing University
Nanjing 210093 (China)
E-mail: ynfan@nju.edu.cn
[b]
Y.-B. Liu, Y.-N. Wang, Dr. H.-M. Lu, Dr. B.-L. Xu, Prof. Y.-N. Fan
Nanjing University-Yangzhou Institute of Chemistry and Chemical
Engineering
Yangzhou 211400 (China)
Supporting information for this article can be found under http://
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Table 1. The alkoxy-carbonylation of EO over Co2(CO)8 and [Co2(CO)6]P4VP catalysts.a
Selectivity (%)e
EG EGDME
EO
Catalyst
-
Promoterd
Conversion (%)e
Other
3-MHP
EM
Products
pyridine
14.7
87.5
98.1
97.8
97.3
98.9
97.6
29.2
85.8
74.3
99.6
0
94.4
10.8
1.8
5.6
1.4
0
0
-
37.2
77.6
74.6
76.5
80.3
78.4
19.1
79.6
73.1
50.9
5.4
7.2
1.3
1.4
0.5
0.5
30.2
5.6
6.6
12.3
45.2
1.7
pyridine
11.7
10.4
11.1
12.3
14.9
36.4
9.1
4-vinylpyridine
9.3
4.4
Co2(CO)8
4-ethylpyridine
8.3
2.7
3-hydroxypyridine
5.7
1.2
imidazole
3.7
2.5
triphenyl phosphine
5.2
9.1
[Co2(CO)6] P4VP
[Co2(CO)6] P4VPb
[Co2(CO)6] P4VPc
-
-
-
3.5
2.2
4.1
10.9
5.3
19.7
1.5
15.6
an(Co):n(EO)=5.7:100, n(EO):n(CH3OH)= 1:1.5, V(THF)=15 mL T=75 oC , t=15 h, Pco =3 MPa. b[Co2(CO)6]P4VP stored in air for a month at 0-4 oC. CWithout using
THF as a solvent. dn(Co):n(promoter)=1:2 eDetermined by GC.
Figure 2. The structure and thermal decomposition of Co2(CO)8 and
[Co2(CO)6]P4VP polymer catalyst.
-carbonylcobalt polymer catalyst containing both the Co2(CO)8
Figure 1. TG curves of Co2(CO)8, P4VP and [Co2(CO)6]P4VP.
catalyst and pyridine promoter has been synthesized and
characterized. Figure 1 and S4 showed the thermogravimetric
(TG) and differential thermal analysis (DTA) results of samples.
catalytic component while pyridine acts as a promoter for the
formation of 3-MHP. It can be seen from Table 1 that EO alkoxy-
carbonylation reaction catalyzed by carbonylcobalt with different
groups substituted-pyridine and imidazole as promoters
exhibited very similar EO conversion and 3-MHP selectivity. In
contrast, the alkoxy-carbonylation of EO catalyzed by Co2(CO)8-
triphenylphosphine gave very lower EO conversion and 3-MHP
selectivity. These results indicated that the carbonylcobalt
catalysts with nitrogen heterocyclic compounds as promoters
were the effective catalysts for alkoxy-carbonylation of EO. The
promotional effect of pyridine on the Co2(CO)8 catalyst will be
For Co2(CO)8 (34.5 wt% Co), three endothermic peaks can be
observed in its DTA curve, the first of which not accompanied
by mass loss, is attributed to melting of Co2(CO)8, while the
second at 98 oC accompanied by mass loss of 17.4 wt% and the
third at 162 oC accompanied by mass loss of 47.1 wt%, are
attributed to decomposition of Co2(CO)8 → Co2(CO)6 → Co ，
respectively (Figure 2). For the P4VP sample pretreated by
o
o
solvothermal method, two peaks appeared at 76 C and 405 C
accompanied by mass loss, the first of which can be attributed to
release of solvents absorbed and/or adsorbed in the polymer,
and, the second to the complete decomposition of the polymer.[8]
As for Co2(CO)8 uploaded P4VP sample, two endothermic peaks
discussed in the later section of poly (4-vinylpyridine)
carbonylcobalt polymer catalyst.
-
o
o
appeared at 67 C and 392 C, which were very similar to those
of bare P4VP. In contrast with DTA curve of bare P4VP sample,
two new endothermic peaks accompanied by mass loss of 13.2
wt% at 240 oC and 7.0 wt% at 305 oC can be observed (Figure
To develop an easily separative and reusable carbonylcobalt
catalyst for alkoxy-carbonylation of EO, the poly (4-vinylpyridine)
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Figure 3. XPS results of [Co2(CO)6]P4VP, Co2(CO)8 and P4VP.
S4 c) in the TG/DTA curves of Co2(CO)8 uploaded P4VP sample,
which are attributed to decomposition of carbonylcoblt in the
sample. Considering that the as-prepared catalyst contained
16.1 wt% Co, it is estimated that total n(CO)/n(Co) molar ratio is
ca. 3:1 (denoted as [Co2(CO)6]P4VP), and the above two new
peaks can be attributed to decomposition of [Co2(CO)6]P4VP→
[Co2(CO)2]P4VP → [Co]P4VP (Figure 2). Compared with
Co2(CO)8, [Co2(CO)6]P4VP decomposition shifts to higher
temperatures, suggesting that there is a strong interaction
between carbonylcobalt and P4VP, which stabilizes the structure
of carbonylcobalt.
The interaction between carbonylcobalt and P4VP in the
[Co2(CO)6]P4VP catalyst has been characterized by using
various methods. X-ray photoelectron spectra (XPS) of the
catalyst (Figure 3) demonstrated the binding energy of Co 2p3/2
in [Co2(CO)6]P4VP was 780.6 eV，which was lower than that of
Co 2p3/2 (781.2 eV) in Co2(CO)8, and the N1s spectra of catalyst
possessed a peak with higher binding energy of 399.4 eV than
that of bare P4VP (398.8 eV), indicating that the electrons
probably transfer from N atoms in part of pyridine rings of
polymer to Co atoms in carbonylcobalt, resulting in formation of
electron-riched Co species in the polymer catalyst.
Figure 5. UV-Vis spectra of [Co2(CO)6]P4VP and Co2(CO)8.
exhibited a red shift from 2003 cm-1 to 1863 cm-1 and the
bridging CO stretching vibration (1825 cm-1) was almost
disappeared, suggesting that there was only terminal CO groups
in the polymer catalyst and their vibrational frequency decreased
obviously. This is probably because the electron-riched Co
transfers more electrons to CO π* antibonding orbit, resulting in
decrease of CO vibrational frequency. The IR absorption band at
1595 cm-1 attributable to the C=N characteristics vibration shifted
to ca. 1603 cm-1 in the polymer catalyst, indicating that the C=N
bonds in pyridine rings became stronger due to N → Co
coordination.[10] From the raman spectra (Figure S5), the 1888
cm-1 of polymer catalyst was clearly assigned to carbonyl
vibration in correspondence with IR spectra (1863 cm-1). On the
other hand, the raman bands in the region of 600-1600 cm-1 are
originated from P4VP, as [Co2(CO)6]P4VP and P4VP have the
same spectroscopic characteristics in this region. Figure 5
showed the UV-Vis spectra of Co2(CO)8 and [Co2(CO)6]P4VP
polymer catalyst. For Co2(CO)8, the bands at 356 nm and 529
nm were assigned to the σ→σ* transitions of Co-Co bond and
the d-d transitions of Co, respectively,[11] and the band at 320 nm
was ascribed to the metal to ligand charge transfer (MLCT) of
Co-CO. For the polymer catalyst [Co2(CO)6]P4VP, the peak
assigned to σ→σ* transitions of Co-Co bond can also be
observed at 356 nm, while Co d-d transitions shifted to higher
wavelength (590 nm). These results clearly confirm that CO
ligands in Co2(CO)8 were partly substituted by pyridine rings
branched to polymer chains. The red shift of Co d-d transitions
band was probably because of weaker ligand field strength of
pyridine than that of CO.[12] Based on the above results, the
The IR spectra of Co2(CO)8 (Figure 4) showed terminal and
bridging C=O stretching vibrations ν(CO) at 2003 cm-1 and 1825
cm-1, respectively.[9] Compared with IR spectra of Co2(CO)8, the
terminal CO stretching vibrations of the polymer catalyst
composition and structure of poly (4-vinylpyridine)
-
carbonylcobalt polymer catalyst was proposed in Figure 2, which
obeys the 18 electron rule. The formation of N→Co coordination
bond not only stabilizes the carbonylcobalt species but also
makes Co to be an electron-riched state.
The catalytic performance of above [Co2(CO)6]P4VP catalyst
for alkoxy-carbonylation of EO has been investigated and the
results are summarized in Table 1. It can be seen that the
polymer catalyst presented high EO conversion (85.8 %) and 3-
MHP selectivity (79.6 %). Even after exposure to air at 0-4 oC for
Figure 4. IR spectra of [Co2(CO)6]P4VP, Co2(CO)8 and P4VP.
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Figure 7. Reusability of the polymer catalyst. (n(Co):n(EO)=5.7:100,
n(EO):n(CH3OH)= 1:1.5, V(THF)=15 mL, T=75 oC , t=15 h, Pco =3 MPa).
Figure 6. Cobalt content in the polymer catalyst after recycles.
a month, the [Co2(CO)6]P4VP catalyst showed a minor drop in
EO conversion (74.3 %) and 3-MHP selectivity (73.1 %),
indicating that the [Co2(CO)6]P4VP polymer catalyst had higher
structure stability. For the polymer catalyst without using THF
as a solvent, the EO conversion increased to 99.6 % and 3-MHP
selectivity decreased to 50.9 %, indicating that THF solvent is
beneficial to the formation of 3-MHP. It's worth noting that the
3-MHP selectivity of [Co2(CO)6]P4VP catalyst was much higher
than Co2(CO)8 catalyst without any nitrogen heterocyclic
compound as a promoter, suggesting that pyridine in the
[Co2(CO)6]P4VP polymer catalyst acts not only as a ligand to
coordinate and stabilize carbonylcobalt but also as a promoter
for the alkoxy-carbonylation of EO. As revealed by the XPS
results mentioned above, the N→Co coordination makes Co in
the carbonylcobalt to be an electron-riched state, which is
Table 2. The alkoxy-carbonylation of various epoxides and alcohols over
[Co2(CO)6]P4VP catalysts.[a]
Epoxides
β-hydroxy esters
Epoxides
Alcohols
CH3-OHb
Conversion (%)c
Selectivity (%)c
92.9
90.4
83.5
73.6
66.4
84.1
71.1
78.0
85.3
84.3
CH3CH2-OH
CH3CH2CH2-OH
CH3-OH
beneficial to nucleophilic attack of Co atoms in carbonylcobalt to
[13]
CH3CH2-OH
carbon atoms in EO,
leading to remarkable increase of 3-
MHP selectivity. As shown in Table 2, the polymer catalyst also
showed excellent catalytic performance for the alkoxy-
carbonylation of other terminal epoxides and alcohols with
different carbon chain length.
CH3CH2-OH
54.9
82.7
Furthermore, the effects of amount of catalyst used and the
an(Co):n(epoxides)=11.4:100, n(epoxides):n(R2-OH)= 1:1.5, V(THF)=15 mL
reaction
conditions
on
the
catalytic
properties
of
T=75 oC, t=15 h, Pco =3 MPa. bn(Co):n(epoxides)=8.6:100. cDetermined by
GC.
[Co2(CO)6]P4VP catalyst for alkoxy-carbonylation reaction of EO
were investigated. As presented in Figure S6, both EO
conversion and 3-MHP selectivity increased remarkably with
increasing the amount of catalyst. On the contrary, the selectivity
of by-products decreased obviously. Figure S7 depicted the
influence of reaction temperature on the catalytic activity and
selectivity. The EO conversion and 3-MHP selectivity increased
remarkably with increase of reaction temperature to 75 oC, but
further increasing temperature resulted in decrease of 3-MHP
Further prolonging reaction time resulted in a minor increase of
EO conversion but obvious decrease of 3-MHP selectivity.
Apparently, the optimum reaction time for alkoxy-carbonylation
of EO catalysed by [Co2(CO)6]P4VP was ca 15 h. As shown in
Figure S9, increasing CO pressure from 1.0 to 4.0 MPa, EO
conversion increased greatly, while 3-MHP selectivity increased
not obviously. It is noteworthy that alkoxy-carbonylation of EO
over [Co2(CO)6]P4VP catalyst can be operated under CO
pressure lower than 3.0 MPa. In comparison, for the
[ILs]+[Co(CO)4]- catalyst, the reaction should be carried out
under CO pressure higher than 3.7 MPa.[2, 3b, 3c]
selectivity.
The
optimum
reaction
temperature
of
[Co2(CO)6]P4VP catalyst for alkoxy-carbonylation of EO was
o
determined to be ca. 75 C. As shown in Figure S8, the alkoxy-
carbonylation of EO over [Co2(CO)6]P4VP catalyst proceeded
rapidly within the first 8 h. After reaction for 15 h, EO conversion
and 3-MHP selectivity reached 85.8 % and 79.6 %, respectively.
The reusability of as-prepared polymer catalyst was
investigated. After reaction for 15 h, the catalyst was readily
separated just by filtration and washed with THF in air. The
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[2] a) T. Haas, B. Jaeger, R. Weber, S. F. Mitchell, C. F. King, Appl. Catal. A.
2005, 280, 83-88; b) S. E. Denmark, M. Ahmad, J. Org. Chem. 2007,
72, 9630-9634; c) R. Weber, U. Englert, B. Ganter, W. Keim, M.
Mothrath, Chem. Commun. 2000, 1419-1420.
catalyst was reused in the following recycle experiments and its
cobalt content was analysed by an inductively coupled plasma
optical emission spectroscopy (ICP-OES) method after every
cycle. As shown in Figure 6 and 7, the cobalt content in the
[3]
a) K. Hinterding, E. N. Jacobsen, J. Org. Chem. 1999, 64, 2164-2165; b)
H. S. Kim, J. Y. Bae, J. S. Lee, C. I. Jeong, D. K. Choi, S. O. Kang, M.
Cheong, Appl. Catal., A. 2006, 301, 75-78; c) J. Liu, J. Chen, C. Xia, J.
Mol. Catal., A. 2006, 250, 232-236; d) J. Liu, H. Wu, L. Xu, J. Chen, C.
Xia, J. Mol. Catal., A. 2007, 269, 97-103; e) M. Allmendinger, M. Zintl,
R. Eberhardt, G. A. Luinstra, F. Molnar, B. Rieger, J. Organomet. Chem.
2004, 689, 971-979.
polymer catalyst decreased within the first
accompanied by decreases of EO conversion and 3-MHP
selectivity. This is probably because there is part of
2 recycles,
a
carbonylcobalt species weakly adsorbed in the fresh polymer
catalyst, which will be inevitably leached out in the first 2
recycles. Interestingly, the cobalt content in the polymer catalyst
remained almost constant after 3 cycles and the EO conversion
and 3-MHP selectivity kept stable, indicating that the
carbonylcobalt species immobilized in the solid polymer
materials through N→Co coordination bonds are very stable and
thus reusable.
In summary, immobilization of carbonylcobalt catalyst by poly
(4-vinylpyridine) (P4VP) through N→Co coordination bonds has
been realized, and as a result, the polymer catalyst exhibited
better catalytic properties and stability than Co2(CO)8 even after
storage in air for a month. The polymer catalyst can be readily
separated by filtration and reused 5 times with only slightly
decreased in EO conversion and 3-MHP selectivity. The
structure of polymer catalyst has been characterized and it has
been proposed that pyridine fragments in the polymer catalysts
act not only as promoters to enhance the catalytic activity and
selectivity for alkoxy-carbonylation of ethylene oxide but also as
stabilizers to increase the reusability of carbonylcobalt species
through N→Co coordination bonds. Our results have revealed
that immobilizing carbonyl-cobalt catalysts in the solid polymer
materials by coordination bonds is a promising strategy to
stabilize the homogeneous catalysts and to easily separate and
reuse them.
[4]
[5]
F.-G. Deng, B. Hu, W. Sun, J. Chen, C.-G. Xia, Dalton Trans. 2007,
4262-4267.
a) Z. Lv, H. Wang, J. Li, Z. Guo, Res. Chem. Intermed. 2010, 36, 1027-
1035; b) Z. Guo, H. Wang, Z. Lv, Z. Wang, T. Nie, W. Zhang, J.
Organomet. Chem. 2011, 696, 3668-3672.
[6]
a) S. C. Bourque, H. Alper, J. Am. Chem. Soc. 2000, 122, 956-957; b)
N. Madhavan, C. W. Jones, M. Weck, Acc. Chem. Res. 2008, 41, 1153-
1165; c) S. Mavila, C. E. Diesendruck, S. Linde, L. Amir, R. Shikler, N.
G. Lemcoff, Angew. Chem. Int. Ed. 2013, 52, 5767-5770.
[7]
[8]
Part of the work is patent pending. CN Pat, CN104841485A, 2015.
a) Y. Su, R. Yan, M. Dan, J. Xu, D. Wang, W. Zhang, S. Liu, Langmuir
2011, 27, 8983-8989; b) K. H. M. Kan, J. Li, K. Wijesekera, E. D.
Cranston, Biomacromolecules 2013, 14, 3130-3139; c) J. A. Moore, S.
Kaur, Macromolecules 1998, 31, 328-335.
[9]
a) R. L. Sweany, T. L. Brown, Inorg. Chem. 1977, 16, 415-421; b) J. P.
Kenny, R. B. King, H. F. Schaefer, Inorg. Chem. 2001, 40, 900-911; c)
F. Hebrard, P. Kalck, L. Saussine, L. Magna, H. Olivier-Bourbigou,
Dalton Trans. 2007, 190-191; d) T. M. Bockman, J. K. Kochi, J. Am.
Chem. Soc. 1989, 111, 4669-4683; e) J. M. Birbeck, A. Haynes, H.
Adams, L. Damoense, S. Otto, ACS Catal. 2012, 2, 2512-2523.
[10] a) M. K. M. Nair, P. K. Radhakrishnan, Synth. React. Inorg. M. 1995, 25,
1077-1089; b) K. H. Wu, Y. R. Wang, W. H. Hwu, Polym. Degrad. Stabil.
2003, 79, 195-200.
[11] a) H. B. Abrahamson, C. C. Frazier, D. S. Ginley, H. B. Gray, J.
Lilienthal, D. R. Tyler, M. S. Wrighton, Inorg. Chem. 1977, 16, 1554-
1556; b) A. Vogler, H. Kunkely, Organometallics 1988, 7, 1449-1450.
[12] P. W. Atkins, Shriver & Atkins' inorganic chemistry, 5th ed. Oxford ;
New York , Oxford University Press, 2010. pp. 473-475.
Keywords: alkoxy-carbonylation of ethylene oxide •
carbonylcobalt catalyst • pyridine promoter • polymer catalyst •
reusability
[13] a) T. L. Church, Y. D. Y. L. Getzler, G. W. Coates, J. Am. Chem. Soc.
2006, 128, 10125-10133; b) J. A. R. Schmidt, E. B. Lobkovsky, G. W.
Coates, J. Am. Chem. Soc. 2005, 127, 11426-11435; c) J. W. Kramer,
E. B. Lobkovsky, G. W. Coates, Org. Lett. 2006, 8, 3709-3712.
[1] a) F. Hebrard, P. Kalck, Chem. Rev. 2009, 109, 4272-4282; b) T. L.
Church, Y. D. Y. L. Getzler, C. M. Byrne, G. W. Coates, Chem.
Commun. 2007, 657-674.
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Chemistry - An Asian Journal
10.1002/asia.201601100
COMMUNICATION
Entry for the Table of Contents
Layout 2:
COMMUNICATION
Yu-Bing Liu,[a, b] Yi-Ning Wang,[a, b] Hai-
Meng Lu,[b] Shuang Liang,[b] Bo-Lian
Xu,[a, b] and Yi-Ning Fan*[a, b]
Page No. – Page No.
Immobilization of carbonylcobalt
catalyst by poly (4-vinylpyridine)
(P4VP) through N→Co coordination
bonds: the promotional effect of
pyridine and the reusability of
polymer catalyst
A recyclable [Co2(CO)6]P4VP polymer catalyst has been synthesized and its
structure has been proposed. It has been demonstrated that the pyridine fragments
in the polymer catalyst act not only as promoters to improve the catalytic
performance for alkoxy-carbonylation of ethylene oxide but also as stabilizers to
increase the reusability of polymer catalyst. Furthermore, the polymer catalyst could
be easily separated by filtration and reused with only slightly loss of catalytic
efficiency.
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