Cu(ii)-catalyzed esterification reaction via aerobic oxidative cleavage of C(CO)-C(alkyl) bonds

Article abstract of DOI:10.1039/c5cc09146b

A novel Cu(ii)-catalyzed aerobic oxidative esterification of simple ketones for the synthesis of esters has been developed with wide functional group tolerance. This process is assumed to go through a tandem sequence consisting of α-oxygenation/esterification/nucleophilic addition/C-C bond cleavage and carbon dioxide is released as the only byproduct.

Full text of DOI:10.1039/c5cc09146b

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Mechanochemical and Solvent-free Assembly of Zirconium-Based
Metal-organic Frameworks
K. Užarević,†,a T. C. Wang,b S.-Y. Moon,b A. M. Fidelli,a J. T. Hupp,b O. K. Farhab,c,* and T. Friščića,*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
organic solvents, achieving reproducibility at expense of
structural defects.16 Thus, the exploitation and potential
commercialisation of excellent materials properties of UiO-66
and analogues remain hindered by adverse synthesis.
We develop the first mechanochemical and solvent-free routes for
zirconium metal-organic frameworks, making the frameworks
UiO-66 and UiO-66-NH2 accessible on gram scale without strong
acids, high temperatures or excess reactants. The frameworks
form either by milling, or spontaneously self-assemble by simply
exposing solid mixtures of reactants to organic vapour. Generated
frameworks exhibit high porosity and catalytic activity in
hydrolysis of model nerve agents, on par with solvothermally
generated counterparts.
Mechanochemistry, i.e. reactivity induced or sustained by
mechanical force,17 has been recently introduced as an
alternative
to
conventional
MOF
syntheses.18
Mechanochemical techniques, such as liquid-assisted grinding
(LAG)19 can enable the synthesis of MOFs20 without bulk
solvents, aggressive conditions and/or corrosive reagents
frequently employed in solution syntheses.21 Importantly,
varying the liquid additive (given as η, ratio of liquid volume to
weight of reactants22) in LAG provides a unique opportunity to
optimise and direct mechanochemical reactions without large
modifications in the milling procedures. Recent applications of
LAG enabled the synthesis of MOFs from poorly soluble metal
oxides and discovery of novel phases.23
Metal-organic frameworks (MOFs)1 are one of the most active
areas of materials science, with proof-of-concept applications
in gas storage and separation,2,3 catalysis,4 chemical defense,5
sensing,6 light harvesting7 and more. Growing impact of MOFs
is reflected by their recent commercialisation, which made a
small number of MOFs based on Mg, Al, Fe, Cu and Zn
commercially available on laboratory research scale.8
However, chemical stability to strong acids or bases, and
retention of microporosity upon extended exposure to
different atmospheres remain central problems for most
MOFs, including those currently being manufactured
commercially.9
We now describe the first implementation of
mechanochemistry and solvent-free ‘accelerated aging’ (AA)24
for the synthesis of zirconium-based MOFs, providing new,
surprisingly simple routes to gram amounts of UiO-66 and its
11,25
amino- analogue UiO-66-NH2
aggressive reagents or high temperatures.
without using bulk solvents,
MOFs based on carboxylate linkers and 12-coordinate
12+
cationic Zr6O4(OH)4
clusters (Figure 1),10 exemplified by
terephthalate-based UiO-6611 and derivatives, have great
potential as catalysts,12 given a high concentration of well-
dispersed metal-based nodes, exceptional aqueous stability
over a range of pH values, high surface areas, and tunable
chemical structures.13 Despite continuous efforts and
improvements,14 however, syntheses of UiO-66 and analogues
remain encumbered by challenging procedures involving
aggressive reagents.11a,15 So far, the most reliable syntheses of
UiO-66 and related MOFs rely on hydrochloric acid in hot
12+
Figure 1. (a)
A
carboxylate-capped Zr6O4(OH)4
cluster; (b) terephthalic and 2-
aminoterephthalic acids; (c) herein developed syntheses of UiO-type MOFs.
Principal requirement for the synthesis of UiO-66 and related
MOFs is the formation of Zr6O4(OH)4 nodes. We considered a
mechanochemical strategy similar to that recently used for
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IRMOFs,26 i.e. reaction of a pre-assembled benzoate cluster after washing and activation was 945 m2 g-1 (Table 1, Figure
Zr6O4(OH)4(C6H5CO2)12
) with terephthalic acid (H2tpa, Figure 3a), consistent with literature.11e,16a,25,31
1). Precursor was readily obtained from zirconium propoxide,
Zr(OPr)4, (see ESI).27 Dry milling of
and H2tpa in correct
(1
1
Table 1. BET surface areas for mechanochemically made zirconium MOFs.a,b
1
stoichiometric ratio 1:6 did not lead to a chemical reaction,
according to powder X-ray diffraction (PXRD) analysis of the
reaction mixture after 90 min milling. Switching to LAG (η=0.66
MOF
UiO-6629
Precursor
BET surface area (m2 g-1)
2
1
2
1020
925
945
890
UiO-66-NH2
UiO-66-NH2
UiO-6629
μL/g22) with N,N-dimethylformamide (DMF) gave
a new
product exhibiting a broad PXRD feature consistent with the
(111) reflection of UiO-66 (Figure 2a-f, also see ESI). Product
formation was accompanied by complete disappearance of
reactant X-ray reflections.
c
Zr(OPr)4
a) Details of activation are given in SI; b) all reactions were done by LAG, using
MeOH as the milling liquid; c) one-pot synthesis from Zr(OPr)4, acrylic acid and
PXRD analysis suggests successful exchange of benzoate H2tpa with MeOH as the grinding liquid.
ligands on , leading to UiO-66 of poor crystallinity. Alternative
precursor based on methacrylic acid, Zr6O4(OH)4(C2H3CO2)12
),28,14c was used as well, without much improvement. At this
1
UiO-66-NH2 was also accessible by LAG from 1, giving a BET
surface area of 925 m2 g-1 (Table 1, Figure S4). Synthesis of
UiO-66-NH2 involved only MeOH as the milling and washing
liquid, again eliminating the need for DMF. Finally, we
(
2
point, we turned to varying the milling liquid. Switching from
DMF to methanol (MeOH) led to little improvement in
crystallinity of product from 1 (Figure 2g). However, LAG of 2
attempted
a one-pot synthesis of UiO-66 directly from
commercial zirconium propoxide, methacrylic acid and
stoichiometric H2tpa. After 90 min, one-pot milling in the
presence of MeOH gave UiO-66 of high surface area (Table 1,
Figures 3a, S5), providing the first one-step route to UiO-66
from zirconium propoxide, an attractive replacement for ZrCl4
and ZrOCl2.
Figure 2. PXRD patterns for LAG syntheses of UiO-66 and UiO-66-NH2: a) H2tpa; b)
precursor 1; c) precursor 2; d) simulated for UiO-66 (CSD RUBTAK); e) LAG of 1 and
H2tpa with DMF; f) LAG of 2 and H2tpa with DMF; g) LAG of 1 and H2tpa with MeOH; h)
LAG of 2 and H2tpa with MeOH; i) UiO-66 made on 3 gram scale by LAG of 2 and H2tpa
with MeOH; j) UiO-66-NH2 made on 1.5 gram scale by LAG of 2 and H2atpa with MeOH.
and H2tpa with MeOH (η=0.66 μ
L/mg22) gave a product whose
PXRD pattern exhibited sharp, well-defined reflections, with
positions consistent with UiO-66 structure (Figure 2h).
Washing was performed with MeOH only, allowing for the first
time complete exclusion of HCl and DMF from the synthesis of
a UiO-type MOF. Using a Spex 8000 mill, synthesis of UiO-66 by
MeOH LAG was accomplished on 3 g scale in 75 min (Figures
2i, S1, S2). BET surface area for the product, calculated from
the N2 sorption isotherm at 77 K, was 1020 m2 g-1 (Table 1,
Figure 3).29 Next, we targeted UiO-66-NH2, based on 2-
aminoterephtalic acid (H2atpa),25 recently established as an
excellent catalyst for hydrolytic degradation of nerve agent
simulants.30 Based on optimised mechanosynthesis of UiO-66,
Figure 3. BET isotherms (N2, 77 K) for: (a) UiO-66 and UiO-66-NH2 from optimised LAG
syntheses using MeOH, and UiO-66 made by one-pot reaction from Zr(OPr)4; (b) UiO-66
and UiO-66-NH2 from AA in MeOH vapour at 45 oC.
we milled
2 and H2atpa in presence of MeOH. After 90 min,
PXRD revealed formation of UiO-66-NH2, isostructural to UiO-
66. Using a Spex 8000 mill, mechanosynthesis of UiO-66-NH2
was performed on 1.5 g scale in 45 min (Figures 2j, S1-S3).
Based on a N2 isotherm at 77 K, BET surface of UiO-66-NH2
We next explored AA, an operationally simple technique
that can achieve solvent-free, low-energy synthesis of metal-
organic materials24 by exposing a physical mixture of reactants
to mild temperature and suitable atmosphere. AA was
2 | J. Name., 2012, 00, 1-3
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previously applied to make salts, cocrystals, metal oxalate catalysis and porosity measurements show that zirconium
MOFs, zeolitic imidazolate frameworks and, recently, HKUST- MOFs made by LAG or AA have properties comparable to
1.24 Short grinding (<1 min in agate mortar) of a physical solvothermally made materials.
mixture of
2 with H2tpa or H2atpa, followed by exposure to
MeOH vapor at 45 °C led to spontaneous assembly of UiO-66
and UiO-66-NH2, respectively (see ESI). Throughout aging,
samples remained solid and products were highly crystalline,
as evidenced by PXRD which revealed complete disappearance
of reactants after 3 days (UiO-66-NH2) and 1 week (UiO-66)
(Figures S6,S7). MOFs, synthesised at >1 g scale, exhibited high
BET areas after activation (Table 2, Figure 3b).
Conclusions
We demonstrated that non-conventional synthetic approaches
of mechanochemistry and accelerated aging enable
a
surprising simplification of procedures for making zirconium-
based MOFs. Frameworks UiO-66 and UiO-66-NH2, noted for
their outstanding stability and catalytic activity, can now be
synthesised on gram scale by a simple, rapid and room-
temperature milling procedure which also allows using
zirconium propoxide as a starting material.
Surprisingly, gram amounts of the microporous MOFs are
obtainable by spontaneous assembly of the organic linker with
a readily accessible carboxylate-capped zirconium cluster,
simply by exposing a physical mixture of reactants to organic
vapour. Herein presented techniques offer a route to highly
porous, catalytically active UiO-frameworks under conditions
resembling mild processes of small molecule self-assembly,
contrasting the conventional approaches that require acidic
reagents (HCl, ZrCl4, ZrOCl2) under solvothermal conditions.
These results have the potential to not only improve the wide
accessibility of UiO-type MOFs but also to change the way
microporous MOFs are synthesised in general.
With the materials in hand, we examined catalytic activity
of UiO-66-NH2 made by LAG and by AA. Both samples show
high hydrolysis activity: 2.5 min and 2 min for an initial half-life
for degradation of the nerve agent simulant dimethyl 4-
nitrophenyl phosphate (DMNP, Figure 4), respectively.
Catalytic activity of
Acknowledgments
We acknowledge NSERC Discovery Grant for funding. KU is
supported by the European Commission and the Croatian
Ministry of Science, Education and Sports from the Marie Curie
FP7-PEOPLE-2011-COFUND program NEWFELPRO, Grant
Agreement No. 62. OKF and JTH acknowledge funding by the
Army Research Office (project no. W911NF-13-1-0229). We
acknowledge Tim Osborne-Jones (Spex SamplePrep LLC) for
providing access to a Spex 8000 mill.
Figure 4. Hydrolysis of nerve agent simulant DMNP: a) reaction; b) hydrolysis profiles in
presence of UiO-66-NH2 made solvothermally (black), by LAG (blue) and AA (red).
UiO-66-NH2 made by AA is comparable to that of
solvothermally prepared material (t1/2=1min);30 the difference
in half-life is attributed to a difference in particle size. For
mechanochemically made UiO-66-NH2, average particle size
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