A copper-phosphonate network as a high-performance heterogeneous catalyst for the CO2 cycloaddition reactions and alcoholysis of epoxides

Article abstract of DOI:10.1039/c7dt00739f

A novel 3D copper-phosphonate network, with the general formula Cu₇(H₁L)₂(TPT)₃(H₂O)₆, namely compound 1, has been synthesized using a rigid tetrahedral linker tetraphenylsilane tetrakis-4-

Full text of DOI:10.1039/c7dt00739f

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Joseph T. Hupp, Omar K. Farha et al.
Efficient extraction of sulfate from water using
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A copper-phosphonate network as high-performance
heterogeneous catalyst for the CO2 cycloaddition reactions and
alcoholysis of epoxide
Received 00th January 20xx,
Accepted 00th January 20xx
Jing Ai,a,b Xue Min,a,c Chao-Ying Gao,a,c Hong-Rui Tian,a Song Dang*a and Zhong-Ming Sun*a

DOI: 10.1039/x0xx00000x
A novel 3D copper-phosphonate network, with the general formula Cu7(H1L)2(TPT)3(H2O)6, namely compound 1, has been
synthesized using a rigid tetrahedral linker of tetraphenylsilane tetrakis-4-phosphonic acid (H8L) and a nitrogen-containing
ancillary ligand (TPT: [5-(4-(1H-1,2,4-triazol-1-yl)phenyl)-1H-tetrazole]) under hydrothermal conditions. The compound was
fully characterized using PXRD, ICP, IR, TGA and elemental analysis. Compound 1 can be used as an efficient catalyst for
the CO2 coupling reaction that is greatly superior to many conventional MOF-based catalysts, where porosity always is
mentioned and used. In addition, it shows excellent catalytic performance for ring-opening reaction with epoxides under
ambient conditions. Additionally, compound 1 can be recycled at least three times without a significant compromise of the
activity in the two catalytic reactions.
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catalysts, were deemed to catalyse the reaction within their
channels, while metal phosphonate with dense network
scarcely ever were employed as heterogeneous catalysts.8,9 As
Introduction
The class of materials known as coordination polymers (CPs) or
metal-organic frameworks (MOFs) has drawn enormous
research interests in recent years because of their appealing
applications in different areas including ion exchange, gas
storage, luminescence, nonlinear optics, catalysis and proton
conduction.1-6 In the broad domain of inorganic–organic hybrid
materials research, since Alberti and coworkers reported the
first metal-organophosphonates in 1978, the chemistry of
metal phosphonates has attracted great attention due to their
high chemical and thermal stability, which are important
factors for their applications.7 In addition, the phosphonate
linkers possess high number of oxygen atoms capable of
bonding to metals to form different structural architectures
while oxygen atoms may still be available to further serve as H-
bond acceptors to generate protonated metal phosphonates
by means of adjusting the pH conditions of reactions. However,
networks based on phosphonate ligation are, by and large, less
studied compared to carboxylate-based counterparts. One
reason why has likely hampered extensive proliferation of
their study as MOFs is the predisposition of metal
phosphonate to a dense motif, thus largely decreasing
opportunities for functions that rely on the porosity, for
example, MOF materials, as the porous heterogeneous
mentioned above, a more diverse set of applications for dense
metal-phosphonate network still remain further to be explored.
In recent years, some MOFs have been demonstrated as
efficient catalysts for the cycloaddition of carbon dioxide to
epoxides and alcoholysis of epoxide. Coupling of CO2 with
epoxides to cyclic carbonate is a useful reaction, as the
abundant C1 resource is conversed to value-added products
both environmentally and practically attractive;10 the
alcoholysis of epoxides with alcohols is
transformation in the synthesis of β-alkoxy alcohols, which are
regarded as useful precursors for wide range of
a significant
a
pharmaceuticals.11 On basis of the catalytic mechanism
proposed in corresponding reports, Lewis acid metal sites and
Brønsted acids sites play the dominant role in catalysis for CO2
conversion and alcoholysis, respectively.12,13 However,
hydrogen-bonding moieties between various catalysts and
epoxides have also been demonstrated to promote CO2
cycloaddition reaction;14 epoxides can also undergo ring-
opening reactions in the presence of Lewis acid.15
Consequently, the protonated metal phosphonate, an
effective combination of Lewis acids and Brønsted acids, would
be a very promising heterogenous catalyst.
In this work, a protonated copper-phosphonate network,
Cu7(H1L)2(TPT)3(H2O)6, namely compound 1, was successfully
prepared. The compound is assembled from a rigid tetrahedral
linker of tetraphenylsilane tetrakis-4-phosphonic acid (H8L), a
nitrogen-containing ancillary ligand of 5-(4-(1H-1,2,4-tri azol-1-
yl)phenyl)-1H-tetrazole (TPT) and Cu(OAc)2. In spite of a dense
motif, the Lewis acid and Brønsted acid sites on the surface of
the compound endowed the catalyst with high-performance
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DOI: 10.1039/C7DT00739F
Fig 1. (a) Ortep representation of the coordination environment in compound
carbon atoms are omitted for clarity. (b) The layer formed by polyhedrons of Cu and P atoms. (c) The 3D view of compound
1
with thermal ellipsoids set at 50% probability. Hydrogen atoms bonded to
1
along the b-axis.
heterogeneous catalytic activity for the coupling of carbon P21/n, and consists of three and
a
half crystallographically
dioxide with epoxides and the ring opening of epoxides with independent Cu(II) ions, one protonated[HL]7- ligand, one and a half
alcohols.
nitrogen-containing ancillary ligands and three water molecules in
the asymmetry unit. Cu1 is in a trigonal bipyramid geometry,
surrounded by four O atoms from one water molecule and three
different phosphonate groups, and one N atom from TPT ligand.
Cu2 and Cu3 are both five-coordinated by three O atoms from three
different phosphonate groups and two N atoms from two TPT
ligand, wherein the two metal ions are bridged by phosphonate O
atom in a vertex-sharing manner. Cu4 has a half occupancy factor
and is four-coordinated by two water molecules and two O atoms
from two phosphonate ligands, thereby forming a rectangle (Fig.
1a). The silicon-based phosphonate ligand links ten copper atoms
through unidentate moieties in two μ2: η1η1, one μ3: η2η1 and one
μ3: η1η1η1 coordination modes (Fig. S1). The three triangle-
bipyramids centered by Cu1, Cu2, Cu3 ions share P atoms to form
one-dimensional (1D) chains. The chains are further connected with
Cu4-centered rectangle to assemble the layers (Fig. 1b), which are
further filled and linked by [HL]7- linkers and TPT ligands to form a
three-dimensional extended dense structure (Fig. 1c).
Coupling reaction of carbon dioxide with epoxides. Styrene oxide
was chosen as the model substrate for the chemical conversion of
CO2 into carbonates to probe the optimized catalytic reaction
conditions (Fig. S7-9). The corresponding results are summarized in
Table 1. Firstly, the reactions were performed using 2 μmol of
compound 1 (5 mg, 0.1 mol ‰ based on catalyst) and 0.3 mmol of
co-catalyst TBAB with 0.1 MPa CO2 at room temperature for
different reaction time: 12h, 24h and 48h. The yields of the
corresponding cyclic carbonate were 1.6%, 2.4% and 4.1%,
respectively (entries 1, 2 and 3 in Table 1). The yields are too low
under those conditions. Then reaction pressure was increased to 1
MPa, only 2.4% yield was obtained. When the temperature was
increased to 60 oC, the yield reached 35.7% as shown in entry 5.
Subsequently, the temperature was raised to 100 oC, keeping the
Experimental section
Materials and methods
All the reagents and solvents were purchased commercially
and used without further purification except for H8L, which
was synthesized according to
documented previously.16
Synthesis of Cu7(H1L)2(TPT)3(H2O)6.(1): A mixture of Cu(OAc)2
(14 mg, 0.07 mmol), H8L(23 mg, 0.035 mmol ), TPT (15 mg,
0.07 mmol) and H2O (8.0 mL) was transferred into a 20mL
Teflon-lined stainless steel autoclave. The autoclave was
sealed and heated at 180 °C for 3 days, and then cooled to
room temperature. The blue rodlike crystals were obtained by
filtration, washed with distilled water several times and dried
at ambient temperature; yield 14 mg (40% based on Cu2+ ions).
Elemental analysis (%) Calcd for compound 1: C 36.87, H 2.13,
N 12.04. Found: C 36.75, H 2.18, N 11.09. IR (KBr, cm−1, Figure
S2): 3134 (s), 3068 (s), 3012 (s), 1621 (m), 1531 (m),1459 (m),
1379 (m), 1288 (m), 1142 (vs), 1056 (vs), 971 (s), 920(s), 849
(m), 814 (m), 764 (m), 668(m), 588 (vs).
a
modified procedure
Cycloaddition of CO2 to epoxides. Crystalline samples 1 were
grinded into powders to be used in the reaction. In a typical
procedure, epoxide (20 mmol), tetrabutylammonium bromide
(TBAB, 97 mg, 0.3 mmol), and the compound
1 (5 mg, 2 μmol)
were placed in a 10 mL stainless steel autoclave. The reactor
was purged with carbon dioxide up to 1MPa under a solvent-
free environment at 100 oC. The yields of the product
carbonates were calculated by 1H NMR spectroscopy.
Ring opening of epoxides with alcohols. Crystalline samples
1
were grinded into powders to be used in the reaction. In a
typical procedure, a mixture of catalyst (5 mg, 2 μmol) and
toluene (27 mg, serving as an internal standard) was added to
a solution of styrene oxide (0.2 mmol) in MeOH (2 mL), and
then the mixture was stirred at ambient temperature. The
reaction was monitored for the required time by GC-7900
equipped with a capillary column (TM-FFAP, 50m × 0.25 mm ×
0.25μm) and a flame ionization detector.
pressure to
1 MPa, the substrates were almost completely
converted to the cyclic carbonates after 12 h of reaction (entry 6).
Besides, the yield of 4-phenyl-1,3-dioxolan-2-one was very low In
the absence of TBAB, indicating that TBAB was imperative for the
reaction (entry 7). Comparably, only 59% yield was obtained using
0.3 mmol TBAB without compound 1 under the same conditions,
the results providing experimental evidence of the important role
of the catalyst 1 in this reaction (entry 8). Accordingly, the
Results and discussion
Structure description. Single-crystal X-ray diffraction analysis
reveals that compound 1 crystallizes in monoclinic space group
2 | J. Name., 2012, 00, 1-3
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Table 1. The coupling reactions of styrene oxide with CO2 under various
maintained. The powder X-ray diffraction (PXRD) of the third run is
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reaction conditions
in good agreement with the PXRD patteDrnOI:o1f0.t1h0e39/aCs7-DprTe0p0a7r3e9dF
compound. The result reveals that the structural integrity of the
compound 1 was retained after cyclic experiment ( Fig. S5).
O
O
O
CO2
O
catalyst, T, P
Moreover, to obtain an insight into the heterogeneous nature of
the compound 1, a filtration test was carried out by removing
the catalyst after 6 hours of reaction, and then the reaction
was further conducted under the same reaction condition
Entry
T(°C)
25
25
25
25
P(MPa)
0.1
0.1
0.1
1.0
1.0
1.0
1.0
1.0
t(h)
12
24
48
12
12
12
12
12
12
12
Yield(%)
1.6
2.4
4.1
1
2
3
4
5
6
7
8
9
10
Table 2. Coupling Reaction of CO2 with Epoxides
O
2.4
CO2
O
60
35.7
> 99
1.9
59
76.9
75.2
O
O
100
100
100
100
100
R
catalyst, T, P
R
Entry
1
Substrate
t(h)
3
Yield(%) TON
TOF
476
O
1.0
1.0
>99
>99
>99
1429
1429
1429
OH
Cl
O
2
3
3
476
119
Reaction conditions: styrene oxide (2.4g, 20 mmol), catalyst (5mg, 2
μmol) and TBAB (97mg, 0.3 mmol) under various conditions. Yields were
determined by 1H NMR spectroscopy.
O
12
optimized reaction condition was found to be 2 μmol of catalyst
and 0.3 mmol of TBAB co-catalyst in solvent-free conditions at 100
oC under 1 MPa CO2 reaction atmosphere.
O
O
4
12
>99
1429
119
Then, a series of different types of the epoxides substrates were
employed to check the catalytic generality of compound 1 for the
chemical conversion of CO2 to form cyclic carbonates under the
optimized reaction conditions (Fig. S10-15 and Fig. S7a, g). As listed
in Table 2, the small-sized epoxide substrates of glycidol and
epichlorohydrin provided an almost complete conversion in 3 hours
with corresponding turnover frequency (TOF) values of 476 per
mole of metal per hour. Relatively, the reaction time for the large
substrates of styrene oxide and 1, 2-epoxy-3-phenoxypropane is
prolonged to about 12 hours with TOF of 119. It is worthwhile to
note that the turnover number (TON) and TOF values of compound
1 for all employed epoxides are much higher than most previously
reported conventional MOF-based catalysts, where porosity always
is mentioned and used (Table S2-5). With the same embedded
Lewis acid metal sites, HKUST-1 was also employed as a
heterogeneous catalyst in these reactions for the sake of
comparison. Although the complete conversions for the
epoxide substrates of glycidol, epichlorohydrin and 1, 2-epoxy-
3-phenoxypropane were equal to those catalyzed by
Reaction conditions in this work: epoxide (20 mmol), catalyst (2 μmol) and
TBAB (0.3 mmol) under CO2 (1 MPa), 100°C. The repeated experiments
after three successive runs, wherein the TBAB was added each time when
compound 1 was recycled.
(Fig. S16-17 and Fig. S7a, g). As recorded in Fig. 2, a slight increase
in the formation of the cyclic carbonate was probably due to the
existence of co-catalyst TBAB, which can also catalyze this reaction
by itself. At the end of the catalytic reaction, inductively coupled
plasma (ICP) analysis was conducted to detect the reaction mixture
filtrate. No Cu leaching demonstrates that the reaction catalyzed by
compound 1 was indeed heterogeneous.
compound
1, a lower yield of 84% for styrene oxide was
obtained, which indicates that the Brønsted acids-containing
1
possesses higher catalytic performance than HKUST-1 in
chemical fixation of CO2 ( Figures S18-21).
Recyclability is another crucial parameter for the heterogeneous
catalysts to be considered for practical applications in industry. The
reusability of compound 1 was carried out by using styrene oxide as
the reaction substrate. The reaction was performed at 100 °C using
2 μmol of catalyst for 12 h. After the reaction, the catalyst was
isolated by centrifugation, washed with dichloromethane for three
times and dried in air. The recovered catalyst was reused in the
following reactions under the same conditions as the first run. After
three circles, the conversion slightly decreased on account of an
unavoidable loss of catalyst during the recyclable reactions,
indicating that the catalytic reactivity of compound 1 was still
Fig. 2. Time-conversion plot for the filtration test of CO2 cycloaddition
reactions; Insert: Recycle experiments with styrene oxide for the
cycloaddition reaction of CO2 with compound 1.
To explore the mechanism of CO2 cycloaddition reaction,
Cu(OAc)2 and H8L were employed for the catalysis in the presence
of TBAB; the yields are 76.9% and 75.2%, respectively (entries 9 and
10 in Table 1), manifesting that both Lewis acids and Brønsted acids
promote the coupling of carbon dioxide with epoxides. Based on
the above results and previous literatures,17 a plausible mechanism
for the CO2 cycloaddition reaction was proposed. As illustrated in
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Scheme 1, the catalytic reaction is initiated via the coordination of the same as the original ones (Fig. S4). And the PXRD patterns
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DOI: 10.1039/C7DT00739F
the metal to the oxygen atom from the epoxide substrate and the showed that the recovered catalyst were consistent with the fresh
Brønsted acid simultaneously forms hydrogen bonding with epoxide,
which assists in activating the epoxy ring. Then the Br− from TBAB
attacks the less sterically hindered carbon atom of the activated
epoxide, leading to the formation of opened epoxy ring.
Subsequently, the CO2 reacts with the oxygen anion of the open
ring to form the epoxide intermediate, which is then converted into
the final cyclic carbonate by the ring closing step. At the same time,
the catalyst is regenerated.
Table 3. Ring opening of styrene oxide with MeOH
Entry
Catalyst
--
1
Cu(OAc)2
H8L
Time/h
12
12
12
0.5
Conversion/% selectivity/%
1
2
3
4
--
--
99
38
99
>99
>99
>99
reaction condtions: styrene oxide (24 mg, 0.2 mmol), catalyst (5 mg, 2
μmol), 25oC, MeOH (2 mL)
sample, indicating that the catalytic activity of
maintained during the recycle experiments (Fig. S5).
1 was still
Conclusion
In summary, a novel three-dimensional copper phos-
phonate network was successfully prepared by a hydrothermal
process. It exhibits prominently catalytic activity for the
cycloaddition of carbon dioxide to epoxides that is superior to
many conventional MOF-based catalysts, where porosity
always is mentioned and used. Besides, it is used as a highly
active and selective heterogeneous catalyst in the ring–
opening reaction with epoxides under ambient conditions.
Considering the high efficiency and the easy preparation of
Scheme 1. Proposed mechanism of the CO2 cycloaddition reaction with
catalyst 1 and TBAB as co-catalyst.
this catalyst system, compound
1 can be an appealing
candidate for many acid-catalyzed reactions in future.
Ring–opening reaction with epoxides. Up to now, there are only
few metal-phosphonate materials which are used as catalysts for
this reaction reported. The catalytic performance of compound 1
was investigated in the ring-opening reaction of styrene oxide. The
results are summarized in table 3. In the absence of catalyst, no
reaction occurred after 12 hours. When the compound 1 was
loaded at 2 μmol (5 mg, 1 mol% based on catalyst), the reaction
gave an excellent conversion (99%) and regioselectivity (>99%) to β-
alkoxy alcohol after 12 hours at room temperature. Compound 1
showed higher selectivity to β-alkoxy alcohol compared to Cu- and
Fe-based MOFs reported in previous literatures for the ring–
opening reaction with epoxides.11c,11e Besides, compound 1 exhibits
higher catalytic activity that is greater than documented metal
phosphonates material catalysts for ring–opening reaction with
styrene oxide under the similar conditions .11d,13
To study the mechanism of catalytic reaction, Cu(OAc)2 and H8L as
catalysts for the ring–opening reaction with epoxides were carried
out under the similar condition. The conversions are 38% and 99%,
respectively. The results suggested that the Brøndsted acid plays a
more dominant role and there is a co-catalytic effect of the Lewis
acid to promote this catalytic reaction. Besides, it is worth noting
that H8L as homogeneous catalyst, although it exhibits superior
activity in this reaction, is limited in separation and reusability,
indicating that this 3D network 1 cannot be replaced by the ligand.
The recyclability of catalyst 1 was examined. Prior to reuse, the
catalyst was centrifuged, washed with dichloromethane and dried
in air. After three circles, the conversion and selectivity keep almost
Acknowledgements
We thank the National Natural Science Foundation of China
(No. 21571171, 21471144, U1407101) and Jilin Province
Natural Science Foundation (20160519004JH, 20150101181JC)
for financial support.
Notes and references
1
(a) B. Aguila, D. Banerjee, Z. Nie, Y. Shin, S. Ma and P. K.
Thallapally, Chem. Commun., 2016, 52, 5940; (b) R. Fu, S. Hu
and X. Wu, Cryst. Growth Des., 2015, 15, 5021.
2
(a) A. Kondo, T. Satomi, K. Azuma, R. Takeda and K. Maeda,
Dalton Trans., 2015, 44, 12717; (b) B. S. Gelfand, J. B. Lin and
G. K. H. Shimizu, Inorg. Chem., 2015, 54, 1185; (c) G. Chang, Z.
Bao, Q. Ren, S. Deng, Z. Zhang, B. Su, H. Xing and Y. Yang, RSC
Adv., 2014, 4, 20230; (d) H. Wang, B. Li, H. Wu, T. L. Hu, Z.
Yao, W. Zhou, S. Xiang and B. Chen, J. Am. Chem. Soc., 2015,
137, 9963; (e) Y. Yan, M. ur ek, F. X. Coudert, N. A.
Vermeulen, S. Grunder, A. Dailly, W. Lewis, A. J. Blake, J. F.
Stoddart and M. chr der, J. Am. Chem. Soc., 2016, 138,3371;
(f) S.Y. Zhang, X. Zhang, H. Li, Z. Niu, W. Shi and P. Cheng,
Inorg. Chem., 2015, 54, 2310.
3
(a) Z. Hu, W. P. Lustig, J. Zhang, C. Zheng, H. Wang, S. J. Teat,
Q. Gong, N. D. Rudd and J. Li, J. Am. Chem. Soc., 2015, 137
,
16209; (b) Z. Guo, X. Song, H. Lei, H. Wang, S. Su, H. Xu, G.
Qian, H. Zhang and B. Chen, Chem. Commun., 2015, 51, 376.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
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Page 5 of 5
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Please do not adjust margins
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ARTICLE
Valente, P. R. Claro, L. D. Carlos, J. Rocha and F. A. A. Paz, J.
4
(a) L. Han, L. Qin, L. Xu, Y. Zhou, J. Sun and X. Zou, Chem.
Commun., 2013, 49, 406; (b) J. Yu, Y. Cui, C. D. Wu, Y. Yang, B.
View Article Online
Mater. Chem. C., 2014, 2, 3311.
DOI: 10.1039/C7DT00739F
Chen and G. Qian, J. Am. Chem. Soc.,2015, 137, 4026; (c) H. 14 (a) A. C. Kathalikkattil, D. W. Kim, J. Tharun, H. G. Soek, R.
Chen, G. Zheng, M. Li, Y. Wang, Y. Song, C. Han, J. Dai and Z.
Fu, Chem. Commun., 2014, 50, 13544.
Roshan and D. W. Park, Green Chem., 2014, 16, 1607; (b) Y.
Ren, X. Cheng, S. Yang, C. Qi, H. Jiang and Q. Mao, Dalton
Trans., 2013, 42, 9930.
5
(a) C. H. Kuo, Y. Tang, L. Y. Chou, B. T. Sneed, C. N. Brodsky, Z.
Zhao and C. K. Tsung, J. Am. Chem. Soc., 2012, 134, 14345; (b) 15 A. C. Gomes, P. Neves, L. C. Silva, A. A. Valente, I. S.
G. J. Chen, J. S. Wang, F. Z. Jin, M. Y. Liu, C. W. Zhao, Y. A. Li
Gonçalves and M. Pillinger, Catal. Sci. Technol., 2016, 6, 5207.
and Y. B. Dong, Inorg. Chem., 2016, 55, 3058; (c) F. Jia, X. 16 A. ch trumpf, . irpi, A. Bulut, F. . orel, . Ranocchiari,
Chen, Y. Zheng, Y. Qin, Y. Tao and X. Wang, Chem. Commun.,
2015, 51, 8504; (d) T. Kiyonaga, M. Higuchi, T. Kajiwara, Y.
. ork, . orlu, . rabowsky, . cesan and Beckmann, J.
Cryst. Growth Des., 2015, 15, 4925.
Takashima, J. Duan, K. Nagashima and S. Kitagawa, Chem. 17 (a) M. North and R. Pasquale, Angew. Chem. Int. Ed., 2009,
Commun., 2015, 51, 2728; (e) Y. B. Huang, Q. Wang, J. Liang,
X. Wang and R. Cao, J. Am. Chem. Soc., 2016, 138, 10104 ; (f)
D. F. Fisac, L. M. A. Díaz, M. Iglesias, N. Snejko, E. G. Puebla,
48, 2946; (b) J. Sun, J. Y. Ren, S. J. Zhang and W. G. Cheng,
Tetrahedron Lett., 2009, 50, 423;(c) J. A. Kozak, J. Wu, X. Su, F.
Simeon, T. A. Hatton and T. F. Jamison, J. Am. Chem. Soc.
2013, 135, 18497.
M. A. Monge and F. ndara, J. Am. Chem. Soc., 2016, 138
,
9089.
6
7
(a) S. Kim, K. W. Dawson, B. S. Gelfand, J. M. Taylor and G. K.
H. Shimizu, J. Am. Chem. Soc., 2013, 135, 963; (b) S. S. Bao, N.
Z. Li, J. M. Taylor, Y. Shen, H. Kitagawa and L. M. Zheng,
Chem. Mater., 2015, 27, 8116; (c) S. Pili, S. P. Argent, C. G.
Morris, P. Rought, V. G. Sakai, I. P. Silverwoo, T. L. Easun, M.
Li, M. R. Warren, C. A. Murray, C. C. Tang, S. Yang and M.
chr der, J. Am. Chem. Soc., 2016, 138, 6352; (d) C. Xiao, Y.
Wang, L. Chen, X. Yin, J. Yin, D. Sheng, Z. Chai, T. E. A. Schmitt
and S. Wang, Chem. Eur. J., 2015, 21, 1.
(a) S. Begum, Z. Wang, A. Donnadio, F. Costantino, M.
Casciola, R. Valiullin, C. Valiullin, M. Bertmer, J. Kärger, J.
Haase and H. Krautscheid, Chem. Eur. J., 2014, 20, 8862; (b) C.
Fang, Z. Chen, X. Liu, Y. Yang, M. Deng, L. Weng, Y. Jia and Y.
Zhou, Inorg. Chim. Acta., 2009, 362, 2101; (c) G. Alberti, U.
Costantino, S. Allulli and N.J. Tomassini, Inorg. Nucl. Chem.,
1978, 40, 1113.
(a) K. J. Gagnon, H. P. Perry and A. Clearfield, Chem. Rev.,
2012, 112, 1034; (b) G. K. H. Shimizu, R. Vaidhyanathan and
J. M. Taylor, Chem. Soc. Rev., 2009, 38, 1430
(a) J. M. Taylor, R. K. Mah, I. L. Moudrakovski, C. I. Ratcliffe,
R. Vaidhyanathan, G. K. H. Shimizu, J. Am. Chem. Soc., 2010,
132, 14055; (b) V. Chandrasekhar, P. Sasikumar and R.
Sasikumar, Dalton Trans., 2008, 5189; (c) T. O. Salami, X. Fan,
P. Y. Zavalij and S. R. J. Oliver, Dalton Trans., 2006, 1574; (d)
P. Z. Li, X. J. Wang, J. Liu, J. S. Lim, R. Zou and Y. Zhao, J. Am.
Chem. Soc., 2016, 138, 2142.
8
9
10 (a) Z. Zhou, C. He, J. Xiu, L. Yang and C. Duan, J. Am. Chem.
Soc., 2015., 137, 15066; (b) A. Decortes, A. M. Castilla and A.
W. Kleij, Angew. Chem. Int. Ed., 2010, 49, 9822; (c) M. H.
Beyzavi, R. C. Klet, S. Tussupbayev, J. Borycz, N. A.
Vermeulen, C. J. Cramer, J. F. Stoddart, J. T. Hupp and O. K.
Farha, J. Am. Chem. Soc., 2014, 136, 15861; (d) J. Song, Z.
Zhang, S. Hu, T. Wu, T. Jiang and B. Han, Green Chem., 2009,
11, 1031; (e) L. Yang, L. Yu, G. Diao, M. Sun, G. Cheng and S.
Chen, J. Mol. Catal. A: Chem., 2014, 392, 278; (f) D. Feng, W.
C. Chung, Z. Wei, Z. Y. Gu, H. L. Jiang, Y. P. Chen, D. J.
Darensbourg and H. C. Zhou, J. Am. Chem. Soc., 2013, 135
17105.
,
11 (a) M. J. Ingleson, J. P. Barrio, J. Bacsa, C. Dickinson, H. Park
and M. J. Rosseinsky, Chem. Commun., 2008, 1287; (b) Y. X.
Zhou, Y. Z. Chen, Y. Hu, G. Huang, S. H. Yu and H. L. Jiang,
Chem. Eur. J., 2014, 20, 14976; (c) A. Dhakshinamoorthy, M.
Alvaro and H. Garcia, Chem. Eur. J., 2010, 16, 8530; (d) S. M.
F. Vilela, D. Ananias, A. C. Gomes, A. A. Valente, L. D. Carlos, J.
A. S. Cavaleiro, J. Rocha, J. P. C. Tomé and F. A. A. Paz, J.
Mater. Chem., 2012, 22, 18354; (e) D. Jiang, T. Mallat, F.
Krumeich and A. Baiker, J. Catal., 2008, 257, 390.
12 B. Li, L. Zhang, Y. Song, D. Bai and H. Jing, J. Mol. Catal. A:
Chem., 2012, 363, 26.
13 S. M. F. Vilela, D. Ananias, J. A. Fernandes, P. Silva, A. C.
Gomes, N. J. O. Silva, M. O. Rodrigues, J. P. C. Tomé, A. A.
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