Highly efficient 3d/4d-4f coordination polymer catalysts for carbon dioxide fixation into cyclic carbonates

Article abstract of DOI:10.1039/c8dt02576b

Two novel highly efficient 3d/4d-4f one-dimensional (1D) double-chain coordination polymer catalysts with unique structures were synthesized for the first time. An X-ray single crystal structure analysis revealed that the two compounds are isomorphous and have a 1D metal-organic network coordination polymer structure. Both compounds also showed significant thermal stability and their structures remained stable up to 325 °C. The reaction conditions, type of substrate, amount of catalyst and its catalytic mechanism were investigated. The catalysts ([Dy₂M₂L₄ (OAc)₂ (MeOH)₅ (H₂O)]) (M = Zn, Cd) exhibited excellent catalytic activity in the cycloaddition of CO₂ and styrene oxide (C₈H₈O, SO). High product yields, high selectivity, and the highest turnover frequency (TOF) of 28 400 h^-1 were achieved. Additionally, the catalysts can significantly enhance the application of the present types of 3d/4d-4f catalysts in catalysis for transformations involving the fixation of CO₂.

Full text of DOI:10.1039/c8dt02576b

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DOI: 10.1039/C8DT02576B
ARTICLE
Highly Efficient 3d / 4d-4f Coordination Polymer Catalyst for
Carbon Dioxide Fixation into Cyclic Carbonates
Gang Wang, Cong Xu, Li Wang, Weisheng Liu*
Received 00th January 20xx,
Accepted 00th January 20xx
Two novel highly efficient 3d/4d-4f one-dimensional (1D) double-chain coordination polymer catalysts with unique
structures were synthesized for the first time. The X-ray single crystal structure analysis revealed that the two compounds
are isomorphous and have a 1D metal-organic network coordination polymer structure. Both compounds also showed
significant thermal stability and their structure remained stable up to 325 °C. The reaction conditions, type of substrate,
DOI: 10.1039/x0xx00000x
www.rsc.org/
amount of catalyst and its catalytic mechanism were investigated. The catalysts ([Dy
Cd) exhibited excellent catalytic activity in the cycloaddition of CO and styrene oxide (C
selectivity, and the highest turnover frequency (TOF) reached 28,400h . Additionally, the catalyst can significantly enhance
the application of the present types of 3d/4d-4f in catalysis for the transformations involving the fixation of CO
M L
2 2 4
(OAc)
2
(MeOH)
5
(H
2
O)]) (M=Zn,
2
8 8
H O, SO). High product yields, high
-
1
2
.
reactivity, low selectivity, air sensitivity and use of additional
solvents, even at high temperature and high pressure (> 5MPa)
Introduction
17-19
conditions
. Therefore, it is especially important to design
Carbon dioxide is the main greenhouse gas, but it is also an
important C1 resource that can be further used. 1-3. Due to its
abundance, non-toxic and inert characteristics, more and more
chemists are paying attention to it. In this regard, the coupling
and synthesize catalysts with high efficiency, high selectivity
and high activity. Research shows that two or more metal
centres near the active site can activate multiple reactants for
superior efficiency and unmatched selectivity. There has been a
great deal of interest in the synergistic effect for controlling the
metal centres in polynuclear complexes to enhance the catalytic
2
of CO and epoxides to form cyclic carbonates is an
environmentally-friendly atomic economic response that
4
-6
reduces CO
2
emissions and conserves energy
. Organic
20-23
performance
. For example, the heteronuclear bimetallic
carbonates, such as dimethyl carbonate and diphenyl
carbonate, which are widely used in the fields of organic
solvents, green reagents and engineering plastics, can be
derived from cyclic carbonates to perform the cycloaddition of
Schiff base Ln-M complex developed by Shibasaki has been used
2
4-
by other groups as a catalyst for various synthesis reactions
.
26
Their results indicate that the proximity of different metal
centres will generate potential synergy, which mainly
contributes to high catalytic reactivity and selectivity.
Additionally, for another, precise control of the supramolecular
structure will modulate the catalytic activity of the catalyst and
expand the scope of the catalyst. The rational design of
heterometallic multinuclear catalysts for further evaluation of
its catalytic performance has great challenges and excellent
CO
2
and epoxides as a commonly used effective approach 7-9
Not surprisingly, green chemistry is the frontier and hot
field of international chemical science research, and CO
catalysis is one of the key branches of green chemistry and
.
2
1
0-12
methodology
2
. CO is both thermodynamically and
kinetically stable, and therefore high-energy reactants and
catalysis are required to overcome these challenges. However,
it can be expedited by transition metal and rare earth salts, and
related coordination compounds that are common catalysts
for the conversion of CO into cyclic carbonates have been a
very effective strategy in previous studies
27-29
prospects
. Motivated by these results, we decided to study
a catalyst that uses a rare earth metal and transition metal as
13
the active catalyst sites for the catalytic conversion of CO
cyclocarbonates.
2
to
2
14-16
. Also, although
With the ultimate goal of obtaining highly efficient
catalysis, we report here the design and synthesis of
heterometallic highly efficient 3d / 4d - 4f coordination polymer
all kind of catalyst systems have been used to catalyse these
reactions, several limitations still exist, such as low catalyst
catalysts featuring ([Dy
2 2 4 2 5 2
M L (OAc) (MeOH) (H O)]) (M=Zn,
Cd). The catalyst has higher reaction activity, selectivity and
a.Key Laboratory of Nonferrous Metal Chemistry and Resources Utilization of Gansu
Province and State Key Laboratory of Applied Organic Chemistry, Key Laboratory
of Special Function Materials and Structure Design, Ministry of Education, College
of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou, 730000,
China.
better substrate universality in the catalytic CO
reaction.
2
cycloaddition
†
Electronic supplementary information (ESI) available: Supporting Fig. S1 – S23 and
Tables S1 – S3 containing additional structural data, characterization details, and Experimental section
catalytic data. CCDC 1815465 – 1815466. For ESI and crystallographic data in CIF or
other electronic format see DOI: xxx-xxx-xxx-xxxx
This journal is © The Royal Society of Chemistry 20xx
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Journal Name
Materials and Characterizations
methanol solution of 0.1 mmol H
Cd(NO ) ·4H O was added and the mixture was stirred for 10
3 2 2
3
L. Then, 0.05 mmol
View Article Online
DOI: 10.1039/C8DT02576B
min to obtain a suspension. To this solution 0.05 mmol
Dy(OAc) ·4H O was added and a clear solution was obtained.
3
2
The mixture was stirred 30 min and filtered for crystallisation at
room temperature. After about two weeks, yellow single
crystals (Fig. S5(b), ESI †) suitable for crystal analysis were
obtained. The abundant complexes powder for catalytic
reaction were collected with the same method used to obtain a
white solid and after filtration, it was washed with acetonitrile,
and dried in the air, to obtain a 45% yield. Further, the products
Scheme. 1. Synthetic routes of complex
1
and complex
2.
2 9 2
were characterized by IR, PXRD and TGA. C113H142Dy N O25Cd :
Elemental analysis (%) found (calculated): C 51.53 (52.68), H
99%) was purchased from 5.43 (5.56), N 4. 75 (4.89). IR (KBr, υ, cm – ) : 3432 (s), 2960(s),
1
Carbon dioxide (CO
2
,
commercial sources and used without further purification. 3,5- 1623(s), 1550 (s), 1460(s), 1383(s), 1250 (s), 1249 (s), 1170 (s),
di-tert-butyl-2-hydroxybenzaldehyde, methyl 5-allyl-3- 1168 (m), 1078 (m), 1027 (w), 844 (w), 815 (w), 743 (m).
methoxysalicylate were purchased from Adamas Reagent, Ltd.
All the epoxides were bought from Sigma–Aldrich, Korea and
the metal salts (>99%) were bought from TCI chemicals. 5-allyl-
X-ray crystallography
Crystal data of Complex 1-2 and H L were collected on
3
2
-hydroxy-3-methoxy benzohydrazide was prepared according SuperNova, Dual, Cu at zero, AtlasS2 system, diffractometer (Cu
30
to the literature method . The infrared spectra were recorded Kα radiation, λ = 1.54178 Å, complex 1, Mo Kα radiation, λ =
on a Burker VERTEX 70 FTIR spectrometer using KBr pellets in 0.71073 Å, complex 2) at 100 K. Data reduction was
the 400-4000cm- region. UV/Vis absorption spectra were accomplished by the CrysAlisPro. Multi-scan absorption
determined on an Agilent Technologies Cary 5000 UV-Vis-NIR corrections were applied by using the program SADABS. The
spectrophotometer. The C, H, and N microanalyses were structure of the compounds was solved by using the direct
1
1
31
measured by Vario EL Cube elemental analyser. The H NMR and method of SHELXTL-2013 and refined by full matrix least-
13
C NMR data were collected on a JNM-ECS 400M NMR squares cycles on F through the Olex2 program 32. The
2
spectrometer. X-ray powder diffraction data were collected on contribution of severely disordered solvent molecules was
PANalytical X'Pert Pro Diffractometer operated at 40 kV and 40 treated as a diffusion treatment by the SQUEEZE program of
33
mA with Cu Kα radiation (λ=1.5406Å). Thermogravimetric PLA-TON and was further refined using the data generated.
analysis experiments were performed using a TGA/NETZSCH All of the non-hydrogen atoms were refined anisotropically. The
STA449C instrument heated from 25-800
℃
(heating rate of 10
℃
organic hydrogen atoms were generated geometrically. For
details, see cif data in Supporting Information. X-ray
crystallographic data and experimental details for all complexes
structural analyses are summarized in Table S1. The CCDC
/min, nitrogen atmosphere).
2 2 4 2 5 2 n
Preparation of [Dy Zn L (OAc) (MeOH) (H O)] · (solvent) (1)
General synthetic procedure for complex (1): 10 μL of reference numbers 1815465 and 1815466 for complex 1 and
triethylamine was added to a 1 mL acetonitrile and 5 mL complex 2.
methanol solution of 0.1 mmol H
Zn(NO ·6H O was added and the mixture was stirred for 10
min to obtain a suspension. To this solution 0.05 mmol
Dy(OAc) ·4H
The mixture was stirred 30 min and filtered for crystallisation at
3
L. Then, 0.05 mmol
Catalytic cycloaddition of CO
2
with epoxides
3
)
2
2
The following general procedure is for the cycloaddition
3
2
O was added and a clear solution was obtained. reaction of CO and epoxides. The reactions were conducted in
2
a
50 mL autoclave reactor. The catalyst, co-catalyst
room temperature. After about two weeks, yellow single tetrabutylammonium bromide (TBAB) and epoxide (10 mmol)
crystals (Fig. S5(a), ESI †) suitable for crystal analysis were were added to the reactor. The reactor was subjected to three
obtained. The abundant complexes powder for catalytic cycles of pressurisation (with CO2 at 1.5 MPa), and
reaction were collected with the same method used to obtain a depressurisation and the final pressure was stabilized at 1 MPa.
white solid and after filtration, it was washed with acetonitrile, The vessel was set in a thermostatic heating jacket, and the
and dried in the air, to obtain a 45% yield. Further, the products solution was mechanically stirred at 800 rpm. Then, the
were characterized by IR, PXRD, and TGA. C117
H
160Dy
2
N
9
O
28Zn
2
:
temperature of the reactor was raised to 120 ℃. After 1 h, the
Elemental analysis (%) found (calculated): C 54.02 (54.13), H reaction was cooled to room temperature, and a small liquot of
–
1
1
6
1
1
.13 (6.21), N 4.79 (4.86). IR (KBr, υ, cm ) : 3435 (s), 2960(s), the reaction mixture was taken for analysis by H NMR in order
623 (s), 1550(s), 1464(s), 1426(s), 1250 (s) , 1173 (m), 1135 (m), to calculate the yield of the reaction.
071 (w), 844 (w), 815 (w), 780 (m).
2 2 4 2 5 2 n
Preparation of [Dy Cd L (OAc) (MeOH) (H O)] · (solvent) (2)
Results and discussion
General synthetic procedure for complex (2): 10 μL
triethylamine was added to a 1 mL acetonitrile and 4 mL
Crystal structure
2
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DOI: 10.1039/C8DT02576B
Fig. 2. TGA curves of complex 1 and 2
at a temperature range of 25-800
℃. Two compounds exhibit
high thermal stability. The results obtained (Fig.2) reveal that
both complexes display a similar thermal behaviour due to their
isomorphous structures. Accordingly, only the thermal stability
of complex 1 is discussed in detail here. The TGA results of
Fig. 1. Structural fragments of complex1. (a) The coordination environment of two
adjacent Dy1, Dy2, and Zn1, Zn2 centres. (b) 1D double-chain structure. (c) Dy1,
Dy2 and Zn1, Zn2 centres coordination polyhedra. (d) Packing diagram along the
compound 1 revealed that the weight loss in this 25-200
℃
interval was 4.7%, mainly due to the loss of solvent molecules
axis showing ten djacent 1D chains. (e) A single chain thermo-ellipsoid model and crystallisation water. When the temperature was up to 325
diagram.
℃
, the second weight loss of 55.8% can be attributed to the
decomposition of the metal-organic network. The third stage of
The X-ray single crystal structure analysis showed that the weight loss occurred mainly from 500
and above, involved a
two compounds are isomorphous and crystallise in the small weight loss, due to decomposition of the framework
monoclinic system, space group P 2 /c (Table S1, ESI †). The formed Dy
, ZnO and carbon residue, which cannot continue
℃
1
2 3
O
structure of the catalyst 1 as a representative example will be to decompose. Thus, the results show that the metal-organic
discussed in detailhere. As shown in Fig.1(a), the Dy1 centre is compounds have excellent thermal stability.
eight-coordinate and has a twisted dodecahedron [DyO
environment, the Dy2 centre has the same coordination
environment, which is filled with two μ -L moieties and two
terminal MeOH ligands. The Dy1 and Dy2 centres are connected has drawn considerable attention in recent years
to six oxygen groups deriving from two μ -L and two MeOH 3d/4d-4f synergistic catalysis system, the two metal centres of
ligand, also two nitrogen groups originating from two μ -L (Fig. Dy and M (Zn, Cd) are located in the proper scope to enable the
(a) and (b), respectively). The Zn1 center is attached to four intramolecular synergistic action, and the exposed polymetallic
6 2
N ]
Catalytic activity for CO
2
fixation
2
The research on the conversion of CO to cyclic carbonate
2
1
, 2
. In this
2
2
1
oxygen groups originating from two μ
oxygen groups are from the MeOH ligand and μ-OA
Zn2 centre is linked to four oxygen groups deriving from two μ
2
-L, and the other two sites act as Lewis acid activators, implying that the catalytic
-
C
anion. The system has potential catalytic applications. In our preliminary
tests, we chose styrene oxide as an epoxide to react with CO
O ligand and and to determine the optimum conditions for this coupling
2
-
2
L, and the other two oxygen groups are from the H
2
-
μ-OA
C
anion. (Fig. 1(a) and (b), respectively). The Dy1 atom is reaction (Table 1). We utilised 0.005 mol% each of catalyst 1 and
double-linked to oxygen and nitrogen groups deriving from two 2, in 0.75 mol% of TBAB as co-catalysts for the cycloaddition of
-L moieties, to form dimer motifs with Zn1, with the shortest styrene oxide and CO
to obtain cyclic carbonate in a solvent-
Dy Zn separation of 7.685 Å, and the Dy-Zn distances free reaction under 120
, at 1 MPa, for 1h. Both catalysts
measured were 7.740 and 7.685 Å for Dy1-Zn1 Dy2-Zn2, achieved excellent yields (60 % and 88 %, respectively) and
μ
2
2
⋯
℃
-1
respectively. (Fig. 1(b) and (c)). These patterns are then further showed high catalytic activity with TOF as high as 17,580 h and
-1
held together through the remaining oxygen and nitrogen 13,984 h after only 1h reaction (Table 1 entries 1-2). Since the
groups of μ
d) and (e)).
2
-L to generate an intricate 1D chain structure (Fig. 1 catalyst 1 showed better catalytic activity, we chose catalyst 1
as a representative catalyst to further investigate the reactions.
(
Various co-catalysts were tested under the same conditions,
with TBAB giving the best result (Table 1 entries 3-5, Fig. 3(a)).
Thermogravimetric analysis
The stability of complex 1and 2 was investigated by Neither catalyst 1 nor TBAB alone could catalyse the reaction
thermogravimetric analysis (TGA) under a nitrogen atmosphere with satisfactory yield (1 % and 25 %, respectively), but the yield
was increased to 93 % when both, catalyst 1 and TBAB, were
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Table 1. Synthesis of cyclic carbonate via insertion of CO
complex 1 and 2 under different conditions a
2
to styrene oxide catalysed by
View Article Online
DOI: 10.1039/C8DT02576B
Cat.
mol%)
Co-cat.
(mol%)
T
Time
(h)
Yield
TOF
-1 b
Entry
Cat.
Co-cat.
(%)b
(
(℃)
(h )
1
2
3
4
5
6
7
8
9
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
0.005
—
Bu
4
4
NBr
NBr
0.75
0.75
0.75
0.75
0.75
—
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
120
140
120
100
80
1
88
60
61
55
69
1
17600
12000
12200
11000
13800
200
Bu
1
Bu
Bu
PPN-Cl
4
NI
1
4
NCl
1
1
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
Bu
4
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
NBr
1
0.25
0.5
1
69
75
88
93
85
25
71
88
92
95
99
99
95
72
42
19
52
78
95
98
99
45
13800
15000
17600
18600
17000
33
1
0.75
1
1
10
1
c
11
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
0.75
1
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
1
0.0025
0.005
0.0075
0.01
1
28400
17600
12267
9500
7920
9900
9500
7200
4200
1900
15600
11700
9500
7538
5964
458
1
1
1
0.0125
0.01
1
1
Fig. 3. The yield of epoxy styrene and carbon dioxide converted to cyclocarbonate under
different reaction conditions. Reaction conditions: (a).10 mmol styrene oxide, 0.005
0.01
1
1
0.01
mol% catalyst, 0.75 mol% co-catalyst, 120℃, 1 h, CO
.005 mol% catalyst, co-catalyst (0-1mol%), 120℃, 1 h, CO
oxide, catalyst (0-0.0125mol%), 0.75 mol% TBAB as the co-catalyst, 120℃, 1 h, CO
MPa. (d).10 mmol styrene oxide, 0.01 mol% catalyst, 0.75 mol% TBAB as the co-catalyst,
temperature (60-140℃), 1 h, CO 1 MPa. (e).10 mmol styrene oxide, 0.01 mol% catalyst,
.75 mol% TBAB as the co-catalyst, 120℃, time (20-100min), CO 1 Mpa.
2
1 MPa. (b).10 mmol styrene oxide,
0.01
1
0.01
60
1
0
2
1 MPa. (c).10 mmol styrene
0.01
120
120
120
120
120
120
20 min
40 min
60 min
80 min
100 min
1
2
1
0.01
0.01
0.01
2
0.01
0
2
H
3
L
0.01
Reaction conditions: (a) styrene oxide (10 m mol ), CO
Determined by H NMR spectroscopy. TOF = Yield/ncat/h. (c). Reaction condition:
2
1 MPa, solvent-free. (b).
results from Table 1 and Fig. 3 revealed that the optimum
conditions for the reaction of CO with styrene oxide are as
follows: the amount of the substrate is 10 mmol, with 0.01
mol% of catalyst and 0.75 mol% of co-catalyst, at 1 MPa and 120
1
2
1
0 mmol styrene oxide, 0.005 mol % catalyst, 0.75 mol %TBAB, CO
2
0.6 MPa.
Selectivity of cyclic carbonates were all >99%.
used as co-catalysts. The yield remains unchanged when the
CO pressure decreased from 1.0 to 0.6 MPa, (Table 1 entries 9
℃
, for 1h to reach a yield of 95%.
In order to evaluate the high catalytic performance of this
2
and 11). With different concentration of TBAB (0.25 mol %, 0.5 3d-4f synergistic catalysis, we compared it with representative
mol %, 0.75 mol % and 1 mol %, respectively) good yields were Zn catalysts and lanthanide complex catalysts under different
-1
-1
obtained with initial TOF as high as 13,800 h , 15,000 h , 17,600 conditions (Table S3). The results revealed that catalyst 1 has
-1
-1
h and 18,600 h (Table 1 entries 7-10, Fig. 3(b)), respectively. higher catalytic activity than most of the tested catalyst
The reaction at different catalyst concentrations (Table 1 including some Zn catalysts and lanthanide catalysts, such as
3
4-36
and lanthanide catalysts 2, 37, 38,
entries 12-17, Fig. 3(c)) showed that the catalyst also had ZnBr
excellent catalytic activity when the amount of catalyst 1 was indicating that the high efficiency of this heterometallic catalyst
.0025 mol% and TBAB was 0.75 mol%, with the highest initial system. Satisfyingly, when the amount of catalyst 1 and co-
2
, Zinc complexes
0
-1
TOF of up to 28,400h . When the amount of catalyst 1 is catalyst TBAB is 0.0025 mol% and 0.75 mol%, respectively, for
0
1
.01mol%, reactions at a different temperature (60
℃
, 80
℃
,
the cycloaddition of styrene oxide under 120 ℃, 1 MPa after
00 , 120 and 140
℃
℃
℃
, respectively) (Table 1 entries 18-22, only 1 h reaction, a medium yield of 71 % was obtained with an
-1
Fig. 3(d)) showed that the catalyst also has outstanding catalytic excellent TOF as high as 28,400 h (Table 1 entry 13), which was
-1
-1
activity with relatively high TOF up to 1,900 h
h
,
4,200 h
12,267 h , respectively. With other conditions TBAB only. This efficiency can be compared with those of the
unchanged, the reaction time from 20 min to 100 min (Table 1 most efficient metal catalysts, such as [EMIm] [Br Zn(Et PO )]
/Zn 40, ZnBr
, Zn-
,
7,200 a clear improvement compared with that of 25 % catalyzed with
-1
-1
-1
, ,
9,500 h
2
2
2
4 2
3
9
36
35
34
entries 23-27, Fig. 3(e)), the conversion of the product was
, [L
1
Zn
2
]
4
, Zn(OPO)
2
42
, Ni(PPh
3
37
)Cl
2
/PPh
3
2
41
2
almost complete after 60min, reaching 95%, so the choice of the CMP , Mg-porphyrin , Yb-DDPY , Ionic Rare Earth Metal , Yb-
reaction time was 60 min for substrate expansion. In short, the
4
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and 50%, respectively) (Table 2 entries, 13, 14 and 15), which
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was ascribed to the steric effect. The results shown in Table 2
indicate that the 3d-4f catalytic system had the higher activity
and displayed broader substrate scopes.
Table 2. Various carbonates from different epoxides catalysed by catalyst 1 under same
condition a
.
Mechanism
Entry
1
Substrte
Product
Yield (%)a
99
TOF(h-1)
9900
2
3
4
5
98
94
99
98
9800
9400
9900
9800
6
7
96
90
9600
9000
Fig. 4. The proposed mechanism for the cycloaddition reactions catalysed by the
catalyst
8
9
95
98
95
9500
9800
9500
In order to determine whether the structure of the catalyst
changes before and after the catalytic reaction, we
characterized the structure of the catalyst by UV/Vis absorption
1
1
1
0
1
2
1
spectroscopy and H NMR (Fig. S9 and Fig. S10), the
1
93
99
9300
9900
spectroscopic (UV/Vis and H NMR) analyses of TBAB, free
3
styrene, free carbonates, H L, before catalysis, and after
catalysis were carried out. UV/Vis absorption spectroscopy
indicates that the structure of the catalyst did not change
1
significantly before and after catalysis. H NMR results show
1
1
3
4
35(93b)
35(90b)
3500(1163)
3500(1125)
that the chemical shift of the catalyst did not change
significantly before and after the contrast reaction. In summary,
the catalyst has good stability and a consistent structure before
and after catalysis.
1
5
3(50b)
300(625)
Based on the results of the multi-metal catalyst systems
37, 38, 44
that have been studied and reported to date
, the
Reaction conditions: (a) 10 mmol epoxide, 0.01 mol% catalyst, 0.75 mol% Bu
as the co-catalyst, 120℃, 1 h, CO 1 MPa. (b) 10 mmol epoxide, 0.01 mol% catalyst,
.75 mol% Bu NBr as the co-catalyst, 120 ℃ , 8 h, CO 1 MPa. Yields were
determined by H NMR. Selectivity of cyclic carbonates were all >99 %.
4
NBr synergistic effect of polymetal systems may originate from
2
different metal systems and a possible approach are proposed
Fig. 4). As shown in Fig. 4, both Zn and Dy ions may play an
0
4
2
(
1
important role in activating the components of the reaction.
n44 The oxygen atom of the epoxy compound first activates the
epoxy ring by binding to Lewis acidic Dy(III) and Zn(II) sites.
4
3
helicate-1(Zn-Tb)38,
mesocate ,
Table S3).
To investigate the wide applicability of the novel 3d-4f
2 n
[Yb(µ-L)(µ3-L)(H O)] Br
(
-
Then, TBAB opened the epoxy ring with Br as a nucleophile to
attack the less-hindered carbon atom of the epoxide.
Subsequently, the open epoxy ring interacts with CO to form
2
catalyst system, a sequence of monosubstituted terminal
epoxides and internal epoxide substrates were examined under
the identical conditions. The results revealed that all the
functionalized terminal epoxides could be obtained with
excellent yields (the yield of most substrates was >90%) and
an alkyl carbonate anion, which is converted to the
corresponding cyclic carbonate by a final ring-closing step, and
finally TBAB is recycled again. In addition, since the Lewis base
4
5-
sites (N atoms) may also promote the cycloaddition reaction
high selectivity (99 %) at 120
2
℃ and 1 MPa of CO pressure,
48
.
H
3
L was used as a catalyst with TBAB for the model reaction.
after only1 h reaction (Table 2 entries 1-12). The internal
epoxides, such as cyclopentene oxide, cyclohexene oxide and
stilbene oxide, exhibited lower activity compared with the
terminal counterparts, but performed with for a relatively long
time to afford the products in reasonably good yields (93%, 90%
The catalytic yield with H L of 45% was significantly improved
3
compared to the 25% yield catalysed with TBAB only (Table 1,
entries 12, 28). Therefore, we hypothesise that the catalysts
may increase the
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ARTICLE
Journal Name
affinity for CO
2
by the incorporation of amide groups into the 10.
S. Klaus, M. W. Lehenmeier, C. E. AndersonVaienwdABrt.icRleiOegnleinre,
Coordination Chemistry Reviews, 2D0O11I:,1205.150,3194/C680D-1T4072597.6B
H. Xu, B. Zhai, C. S. Cao and B. Zhao, Inorg Chem, 2016, 55,
structure and binding to multiple Lewis acid sites, which may
explain the high catalytic activity of the catalyst. The higher
catalytic activity of the catalyst 1 and TBAB system results from
the synergistic effect of combining the Zn ions with the Lewis
11.
12.
13.
14.
15.
16.
17.
18.
19.
9671-9676.
D. Zhao, X.-H. Liu, C. Zhu, Y.-S. Kang, P. Wang, Z. Shi, Y. Lu
and W.-Y. Sun, Chemcatchem, 2017, 9, 4598-4606.
D. Zhao, X. H. Liu, J. H. Guo, H. J. Xu, Y. Zhao, Y. Lu and W.
Y. Sun, Inorg Chem, 2018, 57, 2695-2704.
4
9
acidic Dy(III) sites
.
M. Aresta, A. Dibenedetto and A. Angelini, Chem Rev, 2014,
Conclusions
114, 1709-1742.
C. Maeda, Y. Miyazaki and T. Ema, Catalysis Science &
Technology, 2014, 4, 1482-1497.
Q. Liu, L. Wu, R. Jackstell and M. Beller, Nat Commun, 2015,
In this study, we successfully synthesised two novel 3d/4d-
f 1D double-strand coordination polymer catalysts with unique
structures for CO fixation. The X-ray single crystal structure
2
analysis revealed that the two compounds are isomorphous and
have a 1D metal-organic network coordination polymer. The
topological analysis of the underlying 1D chains allowed us to
establish that all metal atoms of each chain are exposed to the
outside and become potential catalytically active sites. Both
compounds also showed significant thermal stability and their
4
6
, 5933-6933.
J. Sun, S.-i. Fujita, F. Zhao and M. Arai, Green Chemistry,
004, 6, 613-616.
2
T. Ema, Y. Miyazaki, T. Taniguchi and J. Takada, Green
Chemistry, 2013, 15, 2485-2492.
C. J. Whiteoak, N. Kielland, V. Laserna, E. C. Escudero-Adan,
E. Martin and A. W. Kleij, J Am Chem Soc, 2013, 135, 1228-
1231.
M. Raynal, P. Ballester, A. Vidal-Ferran and P. W. van
Leeuwen, Chem Soc Rev, 2014, 43, 1734-1787.
C. J. Brown, F. D. Toste, R. G. Bergman and K. N. Raymond,
Chem Rev, 2015, 115, 3012-3035.
J. N. Rebilly, B. Colasson, O. Bistri, D. Over and O. Reinaud,
Chem Soc Rev, 2015, 44, 467-489.
network remained stable up to 325
showed high catalytic activity (> 95%) and CO
℃
. Importantly, catalyst 1
conversion 20.
2
selectivity (> 99%) to obtain cyclic carbonates with a wide
substrate scopes under suitable conditions. The cycloaddition
reaction between CO and a styrene oxide resulted in TOF up to
2
8,400 h . In addition, the application of the current types of
d-4f catalysts in catalysis are highlighted and particularly,
2
involve the conversion of fixed CO .
21.
22.
23.
24.
-
1
2
3
I. Nath, J. Chakraborty and F. Verpoort, Chem Soc Rev,
2
016, 45, 4127-4170.
R. M. Haak, S. J. Wezenberg and A. W. Kleij, Chem Commun
Camb), 2010, 46, 2713-2723.
(
Conflicts of interest
There are no conflicts to declare.
2
2
5.
6.
J. Park and S. Hong, Chem Soc Rev, 2012, 41, 6931-6943.
S. Matsunaga and M. Shibasaki, Chem Commun (Camb),
2
014, 50, 1044-1057.
2
7.
8.
C. Piguet, M. Borkovec, J. Hamacek and K. Zeckert,
Coordination Chemistry Reviews, 2005, 249, 705-726.
D. E. Barry, D. F. Caffrey and T. Gunnlaugsson, Chem Soc
Rev, 2016, 45, 3244-3274.
Acknowledgements
2
This work was supported by the National Natural Science
Foundation of China (NSFC, Grant 21431002).
29.
D. Zhao, X. H. Liu, Z. Z. Shi, C. D. Zhu, Y. Zhao, P. Wang and
W. Y. Sun, Dalton Trans, 2016, 45, 14184-14190.
K. Cheng, Q. Z. Zheng, Y. Qian, L. Shi, J. Zhao and H. L. Zhu,
Bioorg Med Chem, 2009, 17, 7861-7871.
30.
31.
32.
Notes and references
G. M. Sheldrick, Acta Crystallogr C Struct Chem, 2015, 71,
1.
J. Zhu, T. Diao, W. Wang, X. Xu, X. Sun, S. A. C. Carabineiro
and Z. Zhao, Applied Catalysis B: Environmental, 2017, 219,
3-8.
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard
and H. Puschmann, Journal of Applied Crystallography,
92-100.
2.
3.
4.
5.
6.
7.
Z. Zhao, J. Qin, C. Zhang, Y. Wang, D. Yuan and Y. Yao, Inorg
Chem, 2017, 56, 4569-4576.
J. Ai, X. Min, C. Y. Gao, H. R. Tian, S. Dang and Z. M. Sun,
Dalton Trans, 2017, 46, 6756-6761.
A. Decortes, A. M. Castilla and A. W. Kleij, Angew Chem Int
Ed Engl, 2010, 49, 9822-9837.
C. Y. Gao, H. R. Tian, J. Ai, L. J. Li, S. Dang, Y. Q. Lan and Z.
M. Sun, Chem Commun (Camb), 2016, 52, 11147-11150.
W.-Z. Qiao, H. Xu, P. Cheng and B. Zhao, Crystal Growth &
Design, 2017, 17, 3128-3133.
2
009, 42, 339-341.
A. L. S. P.vander Sluis, Acta Crystallogr. A, 1990, 46, 194-
01.
33.
34.
35.
36.
2
H. Xie, S. Li and S. Zhang, Journal of Molecular Catalysis A:
Chemical, 2006, 250, 30-34.
R. Ma, L.-N. He and Y.-B. Zhou, Green Chemistry, 2016, 18,
226-231.
R. M. Haak, A. Decortes, E. C. Escudero-Adan, M. Martinez
Belmonte, E. Martin, J. Benet-Buchholz and A. W. Kleij,
Inorg Chem, 2011, 50, 7934-7936.
N. Wei, Y. Zhang, L. Liu, Z.-B. Han and D.-Q. Yuan, Applied
Catalysis B: Environmental, 2017, 219, 603-610.
L. Wang, C. Xu, Q.-X. Han, X.-L. Tang, P. Zhou, R. Zhang, G.
Gao, B. Xu, W. Qin and W.-S. Liu, Chemical
Communications, 2018, 54, 2212-2215.
a. W. W. Tao Wang, a Yuan Lyu,*a Xingkun Chen,ac Cunyao
Li,ac Yan Zhang,ac Xiangen Songa and Yunjie Ding*ab, RSC
Adv., 2017, 7, 2836-2841.
3
7.
8.
3
8
.
.
H. Yasuda, L.-N. He and T. Sakakura, Journal of Catalysis,
2
002, 209, 547-550.
M. Ramin, J. Grunwaldt and A. Baiker, Journal of Catalysis,
005, 234, 256-267.
9
2
6
| J. Name., 2012, 00, 1-3
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Pleas De ad l too nn oT tr aa nd sj au cs t ti omn sa rgins
Journal Name
ARTICLE
39.
J. K. Lee, Y. J. Kim, Y.-S. Choi, H. Lee, J. S. Lee, J. Hong, E.-K.
View Article Online
Jeong, H. S. Kim and M. Cheong, Applied Catalysis B:
Environmental, 2012, 111-112, 621-627.
DOI: 10.1039/C8DT02576B
4
4
4
4
4
4
4
4
0.
1.
2.
3.
4.
5.
6.
7.
F. Li, C. Xia, L. Xu, W. Sun and G. Chen, Chemical
Communications, 2003, 0, 2042-2043.
Y. Xie, T. T. Wang, R. X. Yang, N. Y. Huang, K. Zou and W. Q.
Deng, ChemSusChem, 2014, 7, 2110-2114.
T. Ema, Y. Miyazaki, J. Shimonishi, C. Maeda and J. Y.
Hasegawa, J Am Chem Soc, 2014, 136, 15270-15279.
Q. Han, L. Wang, Z. Shi, C. Xu, Z. Dong, Z. Mou and W. Liu,
Chem Asian J, 2017, 12, 1364-1373.
C. Xu, Y. Liu, L. Wang, J. Ma, L. Yang, F. X. Pan, A. M. Kirillov
and W. Liu, Dalton Trans, 2017, 46, 16426-16431.
M. Liu, L. Liang, X. Li, X. Gao and J. Sun, Green Chemistry,
2
016, 18, 2851-2863.
Y. Ren, O. Jiang, H. Zeng, Q. Mao and H. Jiang, RSC
Advances, 2016, 6, 3243-3249.
R. R. Kuruppathparambil, T. Jose, R. Babu, G.-Y. Hwang, A.
C. Kathalikkattil, D.-W. Kim and D.-W. Park, Applied
Catalysis B: Environmental, 2016, 182, 562-569.
L. Liu, S. M. Wang, Z. B. Han, M. Ding, D. Q. Yuan and H. L.
Jiang, Inorg Chem, 2016, 55, 3558-3565.
A. Barthel, Y. Saih, M. Gimenez, J. D. A. Pelletier, F. E. Kühn,
V. D'Elia and J.-M. Basset, Green Chemistry, 2016, 18, 3116-
4
8.
9.
4
3123.
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Graphical abstract
3
3x13mm (300 x 300 DPI)