Effect of the functionalisation route on a Zr-MOF with an Ir-NHC complex for catalysis

Article abstract of DOI:10.1039/c5cc03934g

A new iridium N-heterocyclic carbene (NHC) metallolinker has been synthesised and introduced into a metal-organic framework (MOF), for the first time, via two different routes: direct synthesis and postsynthetic exchange (PSE). The two materials were compared in terms of the Ir loading and distribution using X-ray energy dispersive spectroscopy (EDS), the local Ir structure using X-ray absorption spectroscopy (XAS) and the catalytic activity. The materials showed good activity and recyclability as catalysts for the isomerisation of an allylic alcohol.

Full text of DOI:10.1039/c5cc03934g

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: F. Carson, E.
Martínez-Castro, R. Marcos, G. González Miera, K. Jansson, X. Zou and B. Martín-Matute, Chem.
Commun., 2015, DOI: 10.1039/C5CC03934G.
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
Information for Authors.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the Ethical guidelines still
apply. In no event shall the Royal Society of Chemistry be held
responsible for any errors or omissions in this Accepted Manuscript
or any consequences arising from the use of any information it
contains.
www.rsc.org/chemcomm

Page 1 of 4
ChemComm
View Article Online
DOI: 10.1039/C5CC03934G
Journal Name
RSCPublishing
COMMUNICATION
Effect of the functionalisation route on a Zr–
†
MOF with an Ir–NHC complex for catalysis
Cite this: DOI: 10.1039/x0xx00000x
ab
ac
ac
Fabian Carson, Elisa Martínez-Castro, Rocío Marcos, Greco González
ac
b
*ab
*ac
Miera, Kjell Jansson, Xiaodong Zou and Belén Martín-Matute
Received 00th January 2015,
Accepted 00th January 2015
DOI: 10.1039/x0xx00000x
www.rsc.org/chemcomm
A new iridium
has been synthesised and introduced into a metal–organic MOF) for Suzuki–Miyaura couplings and alkene hydrogenation.
framework (MOF), for the first time, via two different routes: Functionalised NHCs with donor groups on the imidazole sidechain
N-heterocyclic carbene (NHC) metallolinker moieties (prepared by metallation of the imidazolium moieties in the
1
3
1
4
direct synthesis and postsynthetic exchange (PSE). The two can chelate to the metal and improve the catalytic activity. Our
materials were compared in terms of the Ir loading and group recently reported an alcohol-tethered Ir–NHC complex for
1
5
distribution using X-ray energy dispersive spectroscopy hydrogen transfer reactions. The alcohol/alkoxide group participates
EDS), the local Ir structure using X-ray absorption in the catalytic cycle as a Brønsted acid/base and also forms hydrogen
(
1
5b
spectroscopy (XAS) and the catalytic activity. The materials bonds with the reactants. This bifunctional catalyst is therefore an
showed good activity and recyclability as catalysts for the ideal candidate for immobilisation in a MOF because it avoids the use
1
6
isomerisation of an allylic alcohol.
of base additives that can be detrimental to the MOF structure.
We synthesised a new Ir–NHC metallolinker containing an alcohol
donor group, H (Fig. 1 and ESI for full details), and introduced it
into a zirconium MOF, UiO-68–2CH
is constructed from 2',5'-dimethylterphenyl-4,4''-dicarboxylate
dmtpdc) linkers and Zr clusters. Zr–MOFs are ideal as catalyst
MOFs are porous coordination networks assembled from metal and
1
organic units. These materials have been investigated for various
2
L
†
1
7
3
(also known as PCN-56), which
applications including gas storage and separation, biomedicine, and
2
catalysis.
(
1
8
MOFs offer several advantages as supports for transition metal
complexes such as high surface areas, tunable and regularly arranged
3
pore environments. There are several routes to introduce linkers
supports due to their high thermal and chemical stability. In the first
approach, we directly synthesised the MOF from mixture of
dmtpdc and H (Fig. 1, Direct Synthesis). In the second approach,
we introduced into UiO-68–2CH through PSE (Fig. 1,
a
H
2
2
L
containing metal complexes, i.e. metallolinkers, into MOFs. The MOF
4
can be directly constructed from the metallolinker. The multivariate
H
2
L
3
Postsynthetic Exchange). Herein we compare the results between
these two approaches in terms of crystallinity, metal loading,
porosity, metal distribution and catalytic activity of the MOFs.
(
MTV) or mixed-linker approaches allow control of the metallolinker
5
6
7
loading in the MOF. Postsynthetic metallation and PSE or solvent-
assisted linker exchange have been used to introduce many different
metals into MOFs. Although there have been several studies on the
spatial distribution of linkers in MTV-MOFs prepared by direct
The best conditions to synthesise UiO-68–2CH
crystallinity and a high surface area were with ZrCl , H dmtpdc, H
equiv.) and benzoic acid (5 equiv.) in N’-dimethylformamide (DMF)
at 70 °C for 72 h. The X-ray powder diffraction (XRPD) pattern of
UiO-68–2CH matches with the calculated pattern of UiO-68–2CH
Fig. 2a). LeBail refinement using the XRPD data gave a cubic unit
3
with good
4
2
2
O (5
N
,
8
synthesis, there have been few reports concerning the distribution of
1
9
7
c,9
linkers or metallolinkers in MTV-MOFs prepared by PSE.
The
3
3
1
7
distribution of active sites within the MOF will undoubtedly have a
direct impact on its catalytic properties.
(
3
cell,
elemental analysis and thermogravimetric analysis (TGA) suggested
the chemical formula was [Zr (OH) (dmtpdc)5.5∙10H O], with ca. one
out of 12 linkers missing per zirconium cluster (Fig. S3, ESI
For the direct synthesis approach, similar reaction conditions were
used with a ratio of H dmtpdc:H = 60:40.
a = 32.902(1) Å, V = 35619(1) Å (Fig. S2, ESI†). Results from
The σ-electron-donating properties of NHCs as ligands lead to
1
stable metal–NHC complexes, and has resulted in their widespread
0
6
O
5
3
2
2
0
use as catalysts for numerous transformations, including metathesis
†
).
1
1
reactions, cross-couplings, oxidations and water oxidation. There
1
2
have been several reports of metal–NHC complexes in MOFs,
2
2
L
although the only example of catalysis was a MOF containing Pd–NHC
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 1

ChemComm
Page 2 of 4
View Article Online
DOI: 10.1039/C5CC03934G
Fig.
1
Schematic representation illustrating the different routes used to introduce the Ir–NHC metallolinker,
H
2
L
,
into the zirconium MOF.
The functionalised MOF was washed with DMF and ethanol and dried acid linkers (Fig. S5, ESI
under vacuum, yielding a yellow solid referred to as UiO-68–2CH indicated additional linker was present. This implies that some linker
3
direct. XRPD confirmed the crystallinity of the MOF and the diffraction may not be coordinated to the zirconium clusters in UiO-68–2CH -L-
†). In addition, results from elemental analysis
3
-L-
2
1
peaks matched closely with UiO-68–2CH
dmtpdc: was determined to be ~83:17 by H nuclear magnetic [Zr
resonance (NMR) spectroscopy of the digested MOF (MOF treated in
3 3
(Fig. 2a). The actual ratio of PSE. The chemical formula of UiO-68–2CH -L-PSE was estimated as
1
22
L
6
O
4
(OH)
To study the spatial distribution of Ir in the MOFs, we used
-DMSO) (Fig. 2b). These results, together with those from scanning electron microscopy (SEM) and EDS to measure the element
elemental analysis and TGA, indicated the chemical formula of UiO- concentrations (Ir and Zr) inside MOF crystals polished with an argon
4 2 2
(dmtpdc)4.62L1.38∙0.5H L∙10H O].
6
5c
3 4
D PO /d
6
8–2CH
We then tested the PSE route to introduce the metallolinker into direct and UiO-68–2CH
the MOF aiming for a ratio of 60:40 for dmtpdc: . The best conditions distribution of Ir, which ranged from 0.16–0.24 Ir/Zr in UiO-68–2CH
highest loading of metallolinker while avoiding MOF decomposition) direct and 0.34–0.40 Ir/Zr in UiO-68–2CH
involved heating UiO-68–2CH with H in methanol at 60 °C for 24 h. and Table S1, ESI ). The metallolinker loadings calculated using
After washing with methanol and ethanol and drying under vacuum, a different characterisation methods are reported in Table 1. The
yellow, crystalline solid was recovered, and denoted as UiO-68–2CH average Ir loadings estimated by EDS are 19% in UiO-68–2CH
PSE (Fig. 2a). The actual ratio of dmtpdc: in UiO-68–2CH PSE direct and 36% in UiO-68–2CH PSE, which are slightly higher than
3
-
L
-
direct to be [Zr
6
O
5
(OH)
3
(dmtpdc)4.57
L
0.94∙30H
2
O].
ion-beam. EDS measurements on cross-sections of UiO-68–2CH
3
-
L
-
3
-
L
-PSE crystals showed a homogeneous
L
3
-
(
L
-
3
-L-PSE (Figs. S8 and S9
3
2
L
†
3
-
3
-L-
L
-
L
3
-
L
-
3
-L-
1
was ~71:29, which was calculated by H NMR spectroscopy (Fig. 2b). those obtained by inductively coupled plasma optical emission
1
This is closer to the intended ratio of 60:40 compared to the direct spectrometry (ICP-OES) (14 and 27%, respectively) and H NMR
synthesis approach. PSE in DMF gave lower
L
loadings (74:26), and in analysis of the digested MOFs (17 and 29% , respectively).
). We performed Ir III-edge XAS to confirm the integrity of the Ir
complex in the MOF. The X-ray absorption near-edge structure
3
XANES) spectra of H , UiO-68–2CH direct and UiO-68–2CH -L-
water resulted in MOF decomposition (Fig. S1, ESI
†
L
(
2
L
3
-L
-
PSE are similar (Fig. 3), which indicates a similar local coordination
environment around Ir. The extended X-ray absorption fine structure
(
EXAFS) spectra were fitted using crystallographic data from an
1
2
analogous Ir–NHC complex and the results are displayed in Table S2,
ESI . The first and second shells around iridium were included in the
fit and similar distances were attained in H , UiO-68–2CH direct
and UiO-68–2CH PSE, confirming the structure of the Ir–NHC
complex in the MOFs.
UiO-68–2CH was thermally stable up to 400 °C in air according to
TGA measurements (Fig. S3, ESI ). Both UiO-68–2CH direct and
UiO-68–2CH PSE were less stable than UiO-68–2CH and displayed
weight losses at 200 °C, probably corresponding to decomposition of
the Ir–NHC complex. The porosity of the MOFs was studied by N
adsorption (Fig. S14, ESI ). The BET surface area of the MOFs
progressively decreased with increasing metallolinker loading, from
†
2
L
3
-L-
3
-L-
3
†
3
-L-
3
-
L
-
3
2
†
2
2
2
470 m /g for UiO-68–2CH
direct and UiO-68–2CH
We then compared the performance of these materials as
catalysts for the isomerisation of a model allylic alcohol substrate, 1-
3
to 2040 and 1600 m /g for UiO-68–2CH
3
-
L
-
3
-
L
-
PSE, respectively (Table S3, ESI ).
†
2
octen-3-ol. There have been no reports of MOFs as catalysts for the
2
3
Fig. 2 (a) Calculated (black) and observed XRPD patterns of UiO-68–2CH (blue),
1
UiO-68–2CH
spectra of the linkers, H
3
Inspection of the IR spectrum of UiO-68–2CH -L-
3
-
L
-direct (green) and UiO-68–2CH
dmtpdc and H , and the digested MOFs.
PSE revealed a band
3
-L-PSE (red) and (b) H NMR
2
2
L
–
1
at 1687 cm that corresponds to the ν(C=O) stretch of the carboxylic
This journal is © The Royal Society of Chemistry 2013
J. Name., 2013, 00, 1-3 | 2

Page 3 of 4
ChemComm
View Article Online
COMMUNICATION
Journal Name
DOI: 10.1039/C5CC03934G
Table
1 Metallolinker loading in MOFs determined using different
characterisation methods.
1
a
Material
H NMR [%] ICP-OES [%]
EDS [%]
UiO-68–2CH
UiO-68–2CH
3
-L-direct
-L-PSE
17
29
14
27
19
36
3
a
Average of eight positions measured on crystal.
isomerisation of allylic alcohols, although other materials, such as Ru
and Rh complexes supported on alumina and mesoporous silica,
2
3
respectively, have been used to isomerise allylic alcohols.
We compared the catalytic activity of the ester-protected Ir–NHC
metallolinker (see section S6, ESI ), UiO-68–2CH direct and UiO-
8–2CH PSE for the isomerisation of 1-octen-3-ol at 100 °C in
toluene using 4 mol% Ir. The blank reactions (with no catalyst or with
UiO-68–2CH ) gave 0% yield after 24 h (Table 2, entries 1 and 2). The
metallolinker reached >99% yield of 3-octanone after 24 h in the
absence of any additive (Table 2, entry 3). UiO-68–2CH direct and
UiO-68–2CH PSE showed similar catalytic activity, achieving 64%
Fig. 3 Ir LIII-edge XANES spectra of H
PSE.
2 3 3
L, UiO-68–2CH -L-direct and UiO-68–2CH -L-
9
†
3
-L-
6
3
-L-
a
Table 2 Comparison of different catalysts for isomerisation of 1-octen-3-ol.
3
3
-L-
b
3
-
L
-
Entry
Catalyst
Additive
t [h]
Yield [%]
and 65% yield, respectively, after 48 h (Table 2, entries 4 and 5). XRPD
analysis of the MOFs after catalysis showed they retained their
1
2
3
4
5
6
7
8
Blank
UiO-68–2CH
9 (metallolinker)
UiO-68–2CH
UiO-68–2CH
UiO-68–2CH -L-PSE
UiO-68–2CH
UiO-68–2CH
–
–
–
–
–
24
24
24
48
48
24
24
24
0
0
>99
64
65
80
>99
>99
3
crystallinity (Fig. S15, ESI
ppm Ir was present in the supernatant after catalysis with UiO-68–
CH PSE, which indicates that the metallolinker did not leach out
of the material during catalysis. On the other hand, the Ir content in
the supernatant after catalysis was higher (7.5 ppm) for UiO-68–2CH
†). ICP-OES analysis revealed that less than 1
3
-L-direct
-L-PSE
3
c
2
3
-
L
-
AgBF4
NaHCO
K CO
2 3
3
d
3
-L-PSE
-L-PSE
3
d
3
3
-
a
L
-
direct. Therefore, we pursued further catalytic tests with only UiO-
8–2CH PSE. The catalytic activity of UiO-68–2CH PSE was
(10 mol%). This resulted in 80% yield
after 24 h (Table 2, entry 6), although the Ir leaching increased slightly mol%) in toluene prior to the addition of the alcohol. NaHCO or K CO
Reagents and conditions: 1-octen-3-ol (0.1 mmol, 14 µL) and catalyst (4
mol% Ir) were suspended in toluene (1 mL) and stirred vigorously at 100 °C
6
3
-
L
-
3
-L-
b
1
1
2
for 24 or 48 h. Yield of 3-octanone based on H NMR spectroscopy of the
c
improved by adding AgBF
4
4
crude reaction mixture. The MOF was stirred with AgBF (0.01 mmol, 10
d
3
2
3
(
0.1 mmol, 1 equiv.) was added to the reaction.
(
1.7 ppm Ir was detected in the supernatant) and the MOF after
catalysis was less crystalline (Fig. S12, ESI ). Replacing AgBF for
bases, such as NaHCO and K CO , resulted in 99% yield after 24 h
Table 2, entries 7 and 8); however, the Ir leaching was significantly
higher (32 and 5.8 ppm for NaHCO and K CO , respectively) and the
crystallinity of the recovered MOF was affected (Fig. S12, ESI ). This
agrees with our previous findings on the effect of the base on the
†
4
3
2
3
This work was supported by the Swedish Research Council (VR)
and the Swedish Governmental Agency for Innovation Systems
VINNOVA) through the Berzelii Center EXSELENT, Röntgen-
(
3
2
3
(
†
Ångström Cluster though VR, and the Knut and Alice Wallenberg
Foundation (Catalysis in Selective Organic Synthesis and 3DEM-
NATUR). BMM was supported by VINNOVA through a VINNMER
fellowship. EMC and RM thank the Wenner-Gren foundation for post-
doctoral fellowships. Portions of this research were conducted at
beamline I811 (MAX IV Laboratory, Lund, Sweden). We thank Lara
Schultes for the synthesis of organic linkers, Ingmar Persson, Ning
Yuan and Stefan Carlson for their assistance with XAS measurements
and interpretations.
1
6
MOF’s structure, and demonstrates the advantage of immobilising
bifunctional catalysts. On a larger scale experiment and under
otherwise identical conditions as those used in Table 2, entry 5, UiO-
6
8–2CH
3
-L-PSE afforded 99% conversion in the absence of base and
could be recycled three times without any loss in catalytic activity
2
(
4
Table S5, ESI†). The heterogeneity of the catalyst was studied by
filtering the catalyst after 3 h, with no further increase in the yield
after 18 h.
These results demonstrate the importance of the different
functionalisation routes for introducing metal complexes into MOFs
and the effect on the properties and catalytic performance of the
material. PSE is a powerful approach for introducing metallolinkers
into MOFs which, in this case, can lead to higher metal loadings
compared to direct synthesis. The combination of characterisation
methods used here, in particular XAS and EDS, has enabled the
structure and distribution of the metal complex inside the MOF
crystals to be studied. By using a robust zirconium MOF as the
support, together with a highly stable bifunctional Ir–NHC complex, a
porous, recyclable heterogeneous catalyst has been prepared, which
demonstrates that UiO-68 is an ideal MOF for creating advanced
catalytic materials.
Notes and references
a
Berzelii Center EXSELENT on Porous Materials, Stockholm University, SE-106
9
1 Stockholm, Sweden. E-mail: xzou@mmk.su.se, belen.martin.matute@su.se
Department of Materials and Environmental Chemistry, Stockholm University, SE-
06 91 Stockholm, Sweden.
b
1
c
Department of Organic Chemistry, Stockholm University, SE-106 91 Stockholm,
Sweden.
†
Electronic Supplementary Information (ESI) available: synthesis, additional
characterisation data and catalysis details. See DOI: 10.1039/c000000x/
1
2
S. R. Batten, N. R. Champness, X.-M. Chen, J. Garcia-Martinez, S.
Kitagawa, L. Öhrström, M. O’Keeffe, M. Paik Suh and J. Reedijk, Pure
Appl. Chem., 2013, 85, 1715–1724.
(a) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch,
Z. R. Herm, T.-H. Bae and J. R. Long, Chem. Rev., 2012, 112, 724–781;
(b) P. Horcajada, R. Gref, T. Baati, P. K. Allan, G. Maurin, P. Couvreur,
This journal is © The Royal Society of Chemistry 2012
J. Name., 2012, 00, 1-3 | 3

ChemComm
Page 4 of 4
View Article Online
Journal Name
COMMUNICATION
DOI: 10.1039/C5CC03934G
G. Férey, R. E. Morris and C. Serre, Chem. Rev., 2012, 112, 1232–1268; 16 F. Carson, V. Pascanu, A. Bermejo Gómez, Y. Zhang, A. E. Platero-
(
c) J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C.-Y. Su, Chem. Soc.
Prats, X. Zou, B. Martín-Matute, Chem. Eur. J., 2015, DOI:
Rev., 2014, 43, 6011–6061.
10.1002/chem.201500843.
3
4
(a) G. Férey, Chem. Soc. Rev., 2008, 37, 191–214; (b) W. Lu, Z. Wei, Z.- 17 H.-L. Jiang, D. Feng, T.-F. Liu, J.-R. Li and H.-C. Zhou, J. Am. Chem.
Y. Gu, T.-F. Liu, J. Park, J. Park, J. Tian, M. Zhang, Q. Zhang, T. Gentle
III, M. Bosch and H.-C. Zhou, Chem. Soc. Rev., 2014, 43, 5561–5593.
(a) C. A. Kent, B. P. Mehl, L. Ma, J. M. Papanikolas, T. J. Meyer and W.
Soc., 2012, 134, 14690–14693.
18 (a) J. H. Cavka, S. Jakobsen, U. Olsbye, N. Guillou, C. Lamberti, S.
Bordiga and K. P. Lillerud, J. Am. Chem. Soc., 2008, 130, 13850–13851.
Lin, J. Am. Chem. Soc., 2010, 132, 12767–12769; (b) F. Song, C. Wang, 19 We were unable to synthesise crystalline UiO-68 with
J. M. Falkowski, L. Ma and W. Lin, J. Am. Chem. Soc., 2010, 132,
5390–15398.
terphenyldicarboxylic acid (tpdc) using similar synthesis conditions. This
may be due to the poorer solubility of tpdc compared to dmtpdc.
1
5
6
(a) H. Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne, C. B. 20 (a) H. Wu, Y. S. Chua, V. Krungleviciute, M. Tyagi, P. Chen, T.
Knobler, B. Wang and O. M. Yaghi, Science, 2010, 327, 846–850; (b) C.
Wang, Z. Xie, K. E. deKrafft and W. Lin, J. Am. Chem. Soc., 2011, 133,
Yildirim and W. Zhou, J. Am. Chem. Soc., 2013, 135, 10525–10532; (b)
F. Vermoortele, B. Bueken, G. Le Bars, B. Van de Voorde, M.
Vandichel, K. Houthoofd, A. Vimont, M. Daturi, M. Waroquier, V. Van
Speybroeck, C. Kirschhock and D. E. De Vos, J. Am. Chem. Soc., 2013,
135, 11465–11468; (c) S. Øien, D. Wragg, H. Reinsch, S. Svelle, S.
Bordiga, C. Lamberti and K. P. Lillerud, Cryst. Growth Des., 2014, 14,
5370–5372.
1
3445–13454; (c) A. E. Platero-Prats, A. Bermejo Gómez, L. Samain, X.
Zou and B. Martín-Matute, Chem. Eur. J., 2015, 21, 861–866.
(a) E. D. Bloch, D. Britt, C. Lee, C. J. Doonan, F. J. Uribe-Romo, H.
Furukawa, J. R. Long and O. M. Yaghi, J. Am. Chem. Soc., 2010, 132,
1
4382–14384; (b) F. Carson, S. Agrawal, M. Gustafsson, A.
Bartoszewicz, F. Moraga, X. Zou and B. Martín-Matute, Chem. Eur. J., 21 Alternatively, the metallolinker may only be coordinated to zirconium at
1
2
012, 18, 15337–15344; (c) M. Pintado-Sierra, A. M. Rasero-Almansa,
one side and protonated at the other side. In addition, H NMR analysis
A. Corma, M. Iglesias and F. Sanchez, J. Catal., 2013, 299, 137–145; (d)
H. Fei and S. M. Cohen, Chem. Commun., 2014, 50, 4810–4812.
of the supernatant after PSE revealed the presence of H
2
dmtpdc, which
indicates that exchange of the linkers occurred.
7
(a) C. Y. Lee, O. K. Farha, B. J. Hong, A. A. Sarjeant, S. T. Nguyen and 22 (a) N. Ahlsten, A. Bartoszewicz and B. Martín-Matute, Dalton Trans.,
J. T. Hupp, J. Am. Chem. Soc., 2011, 133, 15858–15861; (b) M. Kim, J.
F. Cahill, H. Fei, K. A. Prather and S. M. Cohen, J. Am. Chem. Soc.,
2012, 41, 1660–1670; (b) N. Ahlsten, A. Bermejo Gómez and B. Martín-
Matute, Angew. Chem. Int. Ed., 2013, 52, 6273–6276.
2
012, 134, 18082–18088; (c) S. Takaishi, E. J. DeMarco, M. J. Pellin, O. 23 (a) K. Yamaguchi, T. Koike, M. Kotani, M. Matsushita, S. Shinachi and
K. Farha and J. T. Hupp, Chem. Sci., 2013, 4, 1509–1513; (d) S. Pullen,
H. Fei, A. Orthaber, S. M. Cohen and S. Ott, J. Am. Chem. Soc., 2013,
N. Mizuno, Chem. Eur. J., 2005, 11, 6574–6582; (b) S. Sahoo, H.
Lundberg, M. Edén, N. Ahlsten, W. Wan, X. Zou and B. Martín-Matute,
ChemCatChem, 2012, 4, 243–250.
1
35, 16997–17003.
8
(a) S. Furukawa, K. Hirai, Y. Takashima, K. Nakagawa, M. Kondo, T. 24 The larger scale reaction was carried out using 0.38 mmol of substrate
Tsuruoka, O. Sakata and S. Kitagawa, Chem. Commun., 2009, 5097–
099; (b) X. Kong, H. Deng, F. Yan, J. Kim, J. A. Swisher, B. Smit, O.
instead of 0.10 mmol. The higher yield may be due to better mixing of
the reaction mixture on a larger scale.
5
M. Yaghi and J. A. Reimer, Science, 2013, 341, 882–885.
A. M. Katzenmeyer, J. Canivet, G. Holland, D. Farrusseng and A.
Centrone, Angew. Chem. Int. Ed., 2014, 53, 2852–2856.
9
1
0 (a) W. A. Herrmann and C. Köcher, Angew. Chem. Int. Ed., 1997, 36,
2
2
162–2187; (b) C. M. Crudden and D. P. Allen, Coord. Chem. Rev.,
004, 248, 2247–2273.
1
1 (a) M. N. Hopkinson, C. Richter, M. Schedler and F. Glorius, Nature,
014, 510, 485–496; (b) G. C. Vougioukalakis and R. H. Grubbs, Chem.
2
Rev., 2010, 110, 1746–1787; (c) E. A. B. Kantchev, C. J. O’Brien and M.
G. Organ, Angew. Chem. Int. Ed., 2007, 46, 2768–2813; (d) D. R.
Jensen, M. J. Schultz, J. A. Mueller and M. S. Sigman, Angew. Chem.
Int. Ed., 2003, 42, 3810–3813; (e) I. Corbucci, A. Petronilho, H. Müller-
Bunz, L. Rocchigiani, M. Albrecht and A. Macchioni, ACS Catal., 2015,
5
, 2714–2718.
1
1
2 (a) J. Chun, I. G. Jung, H. J. Kim, M. Park, M. S. Lah and S. U. Son,
Inorg. Chem., 2009, 48, 6353–6355; (b) J. Chun, H. S. Lee, I. G. Jung, S.
W. Lee, H. J. Kim and S. U. Son, Organometallics, 2010, 29, 1518–
1
521; (c) K. Oisaki, Q. Li, H. Furukawa, A. U. Czaja and O. M. Yaghi, J.
Am. Chem. Soc., 2010, 132, 9262–9264.
3 (a) G.-Q. Kong, X. Xu, C. Zou and C.-D. Wu, Chem. Commun., 2011,
4
7, 11005–11007; (b) G.-Q. Kong, S. Ou, C. Zou and C.-D. Wu, J. Am.
Chem. Soc., 2012, 134, 19851–19857.
1
1
4 S. T. Liddle, I. S. Edworthy and P. L. Arnold, Chem. Soc. Rev., 2007, 36,
1
732–1744.
5 (a) A. Bartoszewicz, R. Marcos, S. Sahoo, A. K. Inge, X. Zou and B.
Martín-Matute, Chem. Eur. J., 2012, 18, 14510–14519; (b) A.
Bartoszewicz, G. González Miera, R. Marcos, P.-O. Norrby, and B.
Martín-Matute, ACS Catal., 2015, 5, 3704–3716.
4
| J. Name., 2015, 00, 1-3
This journal is © The Royal Society of Chemistry 2012