Salicylaldimine-based metal - Organic framework enabling highly active olefin hydrogenation with iron and cobalt catalysts

Article abstract of DOI:10.1021/ja507947d

A robust and porous Zr metal - organic framework, sal-MOF, of UiO topology was synthesized using a salicylaldimine (sal)-derived dicarboxylate bridging ligand. Postsynthetic metalation of sal-MOF with iron(II) or cobalt(II) chloride followed by treatment with NaBEt₃H in THF resulted in Fe- and Co-functionalized MOFs (sal-M-MOF, M = Fe, Co) which are highly active solid catalysts for alkene hydrogenation. Impressively, sal-Fe-MOF displayed very high turnover numbers of up to 145000 and was recycled and reused more than 15 times. This work highlights the unique opportunity of developing MOF-based earth-abundant catalysts for sustainable chemical synthesis.

Full text of DOI:10.1021/ja507947d

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Communication
A Salicylaldimine-based Metal-Organic Framework Enables
Highly Active Olefin Hydrogenation with Iron and Cobalt Catalysts
Kuntal Manna, Teng Zhang, Michaël Carboni, Carter W. Abney, and Wenbin Lin
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja507947d • Publication Date (Web): 04 Sep 2014
Downloaded from http://pubs.acs.org on September 11, 2014
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Journal of the American Chemical Society
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A Salicylaldimine-based Metal-Organic Framework Enables Highly
Active Olefin Hydrogenation with Iron and Cobalt Catalysts
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†
†
†
Kuntal Manna, Teng Zhang, Michaël Carboni, Carter W. Abney, and Wenbin Lin*
th
Department of Chemistry, University of Chicago, 929 E 57 St, Chicago, IL 60637, USA
Supporting Information Placeholder
applications in many areas, including gas storage, separation,
ABSTRACT: A robust and porous Zr metalꢀorganic framework,
salꢀMOF, of UiO topology was synthesized using a salicylalꢀ
dimine (sal)ꢀderived dicarboxylate bridging ligand. Postꢀsynthetic
metalation of salꢀMOF with iron(II) or cobalt(II) chloride folꢀ
30ꢀ39
chemical sensing, drug delivery, and catalysis.
In particular,
MOFs have provided an interesting platform for engineering sinꢀ
gleꢀsite solid catalysts for various organic transformations.
40ꢀ49
The pores and channels in MOFs serve as confined space for the
attachment or encapsulation of molecular catalysts, providing
catalytic site isolation and thus preventing bimolecular catalyst
lowed by treatment with NaBEt H in THF resulted in Feꢀ and Coꢀ
3
functionalized MOFs (salꢀMꢀMOF, M=Fe or Co) which are highꢀ
ly active solid catalysts for hydrogenation of alkenes. Impressiveꢀ
ly, salꢀFeꢀMOF displayed very high turnover numbers of up to
145,000 for alkene hydrogenation, and was recycled and reused
more than 15 times. This work highlights the unique opportunity
of developing MOFꢀbased earthꢀabundant catalysts for sustainaꢀ
ble chemical synthesis.
50,51
deactivation.
Incorporation of orthogonal secondary functionꢀ
al groups to MOF backbones allows convenient generation of
different metal complexes, enabling screening and discovery of
novel molecular catalysts. In this work, a MOF containing an
orthogonal salicyladimine (sal) moiety (salꢀMOF) was syntheꢀ
sized and postꢀsynthetically metalated with iron and cobalt salts to
afford robust and highly active singleꢀsite solid catalysts for olefin
hydrogenation.
salꢀMOF was constructed from the dicarboxylate bridging ligꢀ
and, salꢀTPD (Scheme 1) and the Zrꢀbased secondary building
unit (SBU) to afford a UiO framework of Zr O (OH) (salꢀ
Although precious metal complexes dominate the homogeneꢀ
ous catalysis literature, few of them have found industrial applicaꢀ
tions owing to their high price and inherent toxicity. The reꢀ
1
6
4
4
52ꢀ54
TPD)6.
UiOꢀtype MOFs have been used for many catalytic
placement of precious metals with earthꢀabundant and less toxic
elements, i.e., base metals, is thus at the forefront of contempoꢀ
rary molecular catalysis, with significant progress being made in
51,55,56
reactions owing to their excellent stability.
H salꢀTPD was
2
synthesized from 2,5ꢀdibromoaniline as shown in Scheme 1 with
an overall yield of 14%.
2ꢀ9
the past few years. Nevertheless, homogeneous catalysts conꢀ
taining base metals are prone to deactivation via intermolecular
pathways. Steric protection around the metal centers by elaborateꢀ
ly designed, sterically hindered ligands is a common strategy for
designing stable catalysts, often at the expense of catalytic activiꢀ
ties. Immobilization of homogeneous catalysts in structurally
regular porous solid supports can provide catalytic site isolation
without relying on bulky ligands, thus offering an alternative
route to obtaining highly active base metal catalysts. Such solid
catalysts can be also readily recovered and reused, mitigating
undesired metal leaching into the organic products. Herein we
report the first use of a metalꢀorganic framework (MOF) for imꢀ
mobilizing highly active Fe(II)ꢀ and Co(II)ꢀsalicylaldimine cataꢀ
lysts for hydrogenation of alkenes.
a
Scheme 1. Synthesis of H sal-TPD.
2
a
Hydrogenation of olefins is one of the most important reactions
in organic synthesis, though many industrially important hydroꢀ
Reagents: (i) Pd(OAc) , CsF, PPh , THF, reflux, 12 h, 25%
2 3
yield; (ii) KOH, MeOH, THF, 12 h, rt, and then TFA, THF, 2 h,
rt, 90% yield; (iii) salicylaldehyde, DMSO, MeOH, 12 h, 60%
yield.
10
genation reactions still rely on precious metal catalysts. Signifiꢀ
cant efforts have in recent years been devoted to discovering
earthꢀabundant metal catalysts, particularly based on iron and
salꢀMOF was synthesized by heating ZrCl and H salꢀTPD in a
5
,11ꢀ19
4
2
cobalt complexes,
but many of these catalyst systems have
DMF solution in the presence of trifluoroacetic acid. Single crysꢀ
tal Xꢀray diffraction studies reveal a UiOꢀtype structure for salꢀ
limited lifetimes and modest activities. Parallel efforts have been
devoted to the development of zeoliteꢀ and silicaꢀsupported ironꢀ
ꢀ
2
0,21
MOF, which crystallizes in the Fm3m space group and contains
and cobaltꢀbased heterogeneous hydrogenation catalysts,
bare
2
2ꢀ28
both octahedral and tetrahedral cages with edges measuring 15 Å.
or protected metallic nanoparticles,
or iron oxide nanopartiꢀ
29
The asymmetric unit consists of 1/48 of the Zr O (OH) (O CR)12
6 4 4 2
cleꢀbased catalysts. However, the activities and lifetimes of
these heterogeneous hydrogenation catalysts are still far from
satisfactory.
SBUs and 1/8 of the bridging ligands. As the sal groups could not
be accurately located on the electron density map due to partial
decomposition of H salꢀTPD during MOF synthesis and crystalꢀ
2
As a new class of porous molecular materials, MOFs have atꢀ
tracted increasing interest in recent years owing to their potential
lographic disorder of the side chains, the presence of the sal moieꢀ
1
ty in the MOF was instead established and quantified by H NMR
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spectra of digested MOF samples. NMR studies consistently reꢀ
vealed ~80% of the sal moiety remains intact in the salꢀMOF
under the synthesis conditions (Figure S4, supporting information
Due to disorder and incomplete functionalization and metaꢀ
1
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lation of the salꢀMOF, the Fe coordination environment in salꢀFeꢀ
MOF cannot be studied by Xꢀray crystallography. Instead, we
performed Xꢀray absorption spectroscopy (XAS) at the Fe Kꢀedge
to investigate the Fe coordination environment. A model of the
preꢀcatalyst was generated based on the single crystal structures
[
SI]). The powder Xꢀray diffraction (PXRD) pattern of salꢀMOF
is identical to the pattern simulated from the single crystal strucꢀ
ture (Figure 1d). Nitrogen sorption measurements indicate salꢀ
2
57
MOF is highly porous with a BET surface area of 3311 m /g and
of Fe (sal) Cl (THF) (Figure 2a; see below) and Fe(tꢀBusal) .
4
4
4
2
2
pore sizes of 8.2 Å and 11.1 Å (Figure 1b; Figure S10, SI)
Fitting the extended Xꢀray absorption fine structure (EXAFS)
region of the XAS spectrum with the structure model reveals a
Fe(II) complex containing the sal moiety, one chloride, and two to
three THF solvent molecules as ligands (Figure 1c). DFT calculaꢀ
tions suggest minimal energy differences (~2.5 kcal/mol) between
fiveꢀ and sixꢀcoordinate Fe(II) structures (Figure 2b). As EXAFS
fits the average coordination environment for all Fe atoms in the
sample, it is reasonable that the sample contains a mixture of fiveꢀ
and sixꢀcoordinate species, presumably due to the ease of losing
coordinated THF molecules during sample handling.
a)
0
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0
Cl
MCl
2
(THF)
x
M
N
OH
THF
N
O
sal-MOF
sal-M-MOF
(M = Fe, Co)
1
200
000
800
600
b)
1
c)
5
0
absorption
desorption
4
00
00
0
magnitude (exp)
magnitude (fit)
real component (exp)
real component (fit)
2
-5
0.0
0.2
0.4
0.6
0.8
1.0
0
1
2
3
4
5
p/p0
R (Å)
d)
sal-MOF (simulated)
sal-MOF (experimental)
sal-Fe-MOF (fresh)
sal-Fe-MOF (after run 1)
sal-Fe-MOF (after run 5)
e)
sal-Co-MOF (after hydrogenation)
sal-Co-MOF (fresh)
sal-MOF (fresh)
Figure 2. Crystal structure of Fe
(sal) Cl (THF) (left) and DFT
4 4 4 2
calculated structure of Fe(sal)Cl(THF) (right).
3
Table 1: Optimization of reaction conditions for sal-Fe-MOF
a
catalyzed hydrogenation of 1-octene.
sal-Fe-MOF
10
20
30
40
0
10
20
30
40
40 atm H , 23 °C
2
2θ
2θ
Entry
Catalyst
Solvent
Time
Yield (%)
Treatment
Figure 1. a) Postꢀsynthetic metalation of salꢀMOF to form salꢀMꢀ
MOFs. b) Nitrogen sorption isotherm of salꢀMOF. c) Experiꢀ
mental EXAFS spectra at the Fe Kꢀedge of salꢀFeꢀMOF and fits
in Rꢀspace showing the magnitude (solid squares, solid line) and
real component (hollow squares, dash line) of the Fourier Transꢀ
form. d) PXRD pattern simulated from the CIF file (black), and
PXRD patterns of pristine salꢀMOF (blue), freshly prepared salꢀ
1
2
3
4
5
6
7
NaBEt H
THF
THF
16 h
18 h
18 h
18 h
16 h
16 h
16 h
100
0
3
nꢀBuLi
EtMgCl
THF
0
Et Zn
2
THF
0
b
NaBEt H
THF
100
3
st
th
c
b
FeꢀMOF (red), salꢀFeꢀMOF recovered from the 1 (pink) and 5
NaBEt H/Hg
THF
100
3
run (purple) of 1ꢀoctene hydrogenation. e) PXRD patterns of prisꢀ
tine salꢀMOF (black), freshly prepared salꢀCoꢀMOF (red), and
salꢀCoꢀMOF recovered from hydrogenation of 1ꢀoctene (blue).
b
NaBEt H
toluene
92
3
a
Reaction conditions: 3.0 mg salꢀFeꢀMOF (0.1 mol% Fe), 0.8
b
mol% cat. treatment, 1.56 mmol 1ꢀoctene, 0.5 mL solvent. 0.01
Postꢀsynthetic metalation was performed by treating salꢀMOF
c
mol% Fe. One drop of Hg was added before adding 1ꢀoctene.
with 5.0 equiv of FeCl2•4H O in THF to afford salꢀFeꢀMOF as a
2
brown solid, or with 7.0 equiv of CoCl in THF to afford salꢀCoꢀ
Conditions for hydrogenation were optimized by treating salꢀ
FeꢀMOF with several organometallic reagents. Upon treatment
2
MOF as a greenish blue solid. Crystallinity of salꢀMOF was mainꢀ
tained upon metalation as evidenced by similar PXRD patterns of
salꢀMOF and salꢀMꢀMOFs (Figures 1d & 1e). Inductively couꢀ
pled plasmaꢀmass spectrometry (ICPꢀMS) analyses of the digestꢀ
ed metalated MOFs provided Fe and Co loadings of 66% and 6%
for salꢀFeꢀMOF and salꢀCoꢀMOF, respectively. The Co loading
with NaEt
hydrogenation of olefins. Treatment of 0.01 mol% salꢀMOFꢀFe
with NaBEt H (8 equiv w.r.t. Fe) in THF for 1 h followed by
washing with THF led to a highly active hydrogenation catalyst
that completely converted 1ꢀoctene to nꢀoctane under 40 atm H
BH in THF, salꢀFeꢀMOF is a highly active catalyst for
3
3
2
1
increased to 80% when the MOF was first treated tꢀBuOK. H
at room temperature in 18 h. The rate of hydrogenation was unꢀ
changed in the presence of mercury (Table 1, entry 6), which
suggests that in situꢀgenerated Fe nanoparticles were not responꢀ
sible for the observed catalysis and that Feꢀhydride is the active
species. Additionally, salꢀFeꢀMOF displayed higher catalytic
activity in THF compared to methylene chloride and hydrocarbon
solvents. Impressively, under the optimized reaction conditions,
NMR spectra of digested salꢀFe and salꢀCo MOFs showed that
the sal moiety remained intact within the MOFs upon metalation.
salꢀFeꢀMOF and salꢀCoꢀMOF give BET surface areas of 3101 and
2
3
366 m /g, respectively, with pore size distributions remaining
essentially unchanged from pristine salꢀMOF (Figures S8ꢀS10,
SI). The surface area and pore aperture dimensions confirm the
presence of open channels in the MOF, which suggests the Fe and
Co sites are accessible to alkenes during catalytic reactions.
5
salꢀFeꢀMOF gave a turnover number (TON) of 1.45×10 for the
hydrogenation of 1ꢀoctene (Table 2, entry 2).
2
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salꢀFeꢀMOF displayed excellent activity in the hydrogenation
linity (Figure 1d). Excellent yields (89ꢀ99%) of nꢀoctane were
obtained consistently in the reuse experiments with no observaꢀ
tion of alkene isomerization or other byproducts. The catalytic
activity of salꢀFeꢀMOF dropped significantly after run 9 and poor
conversion of 1ꢀoctene was observed at run 11 even after a longer
reaction time (Figure 3). Interestingly, the catalyst could be reꢀ
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
of a wide range of aliphatic and aromatic terminal alkenes (Table
2). At 0.05ꢀ0.01 mol% catalyst loading, styrene and other alkoxyꢀ
and halogenꢀfunctionalized substrates were hydrogenated with
complete conversion, affording the corresponding products in 93ꢀ
00% yield (Table 2, entries 4, 7, and 8). Importantly, a TON of
4000 was obtained for hydrogenation of styrene. salꢀFeꢀMOF
1
4
generated by simply treating with 10 equiv. of NaBEt H followed
3
also displayed high TONs and excellent yields for the hydrogenaꢀ
tion of gemꢀdisubstituted alkenes, such as αꢀmethyl styrene, and
dialkenes such as 1,7ꢀoctadiene and allyl ether (Table 2, entries
10, 12, and 14). Although the internal olefin, cyclohexene, was
readily hydrogenated, cisꢀβꢀmethyl styrene required longer reacꢀ
tion times. salꢀFeꢀMOF is tolerant of aldehyde, ketone, and ester
functional groups. Functionalized alkenes such as dimethyl itaꢀ
conate, allyl acetate and methylacrylaldehyde were selectively
reduced to dimethyl 2ꢀmethylsuccinate, propyl acetate, and isobuꢀ
tyraldehyde, respectively (Table 2, entries 18, 19, and 21).
by washing with THF. The regenerated MOF catalyst could be
recovered and reused another 6 times before further deactivation.
The decrease in activity could be attributed to multiple factors
including cumulative iron site deactivation by trace amounts of air
or water and diminished MOF crystallinity following repeated
recycling and reuse experiments. The heterogeneity of salꢀFeꢀ
MOF was confirmed by several experiments. The PXRD patterns
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
st
th
of salꢀFeꢀMOF recovered from the 1 and 5 run remained unꢀ
changed from that of pristine salꢀFeꢀMOF (Figure 1d), indicating
the stability of the MOF framework under the catalytic condiꢀ
tions. Additionally, ICPꢀMS analyses showed that the amounts of
Fe and Zr leaching into the supernatant after the 1st run were
a
Table 2: Sal-M-MOF catalyzed hydrogenation of olefins.
th
R1
0.074% and 0.004%, respectively, and after the 4 run were
R1
sal-M-MOF
40 atm H2
THF, 23 °C
0.069% and 0.003%, respectively. Moreover, no further hydroꢀ
genation was observed after removal of salꢀFeꢀMOF from the
reaction mixture (Scheme S2, SI). An additional control experiꢀ
R3
R3
R2
R2
ment was performed with only FeCl and NaBEt H at a loading
Entry Substrate
M
Time % Yield TON
2
3
equivalent to the amount of iron leached from the MOF. No conꢀ
version was observed by NMR spectroscopy, showing that the
leached iron species is not responsible for the catalytic activity.
1
2
3
Fe
18 h
8 d
18 h
100
94
75
10000 b
145000
25000
Co
Fe
100
4
5
6
18 h
24 h
18 h
100
44
55
10000c
44000
18300
80
Co
Fe
d
7
48 h
100
>20000
60
40
20
0
4
4
-FC H
6 4
8
9
Fe
Co
24 h
18 h
100
100
>10000
-OMeC H
6
4
e
>2000
1
1
0
1
Fe
Co
18 h
18 h
100
100
>10000
>2000
e
0
5
10
15
20
e
Run
12
Fe
Co
24 h
18 h
100
100
>2000e
1
3
>2000
Figure 3. Plot of yield (%) of nꢀoctane at various runs in the reꢀ
cycle and reuse of salꢀFeꢀMOF (0.5 mol% Fe) for hydrogenation
of 1ꢀoctene. SalꢀFeꢀMOF was regenerated after run 11 and run 18
f
1
4
O
Fe
24 h
100
>1000
f
by treating with NaBEt H in THF.
3
1
1
5
6
Fe
Co
18 h
18 h
100
100
>1000e
>2000
salꢀCoꢀMOF is also active in olefin hydrogenation upon treatꢀ
ment with 8 equiv. of NaBEt H in THF. At 0.05 mol% Coꢀ
3
f
f
1
1
7
8
Fe
Fe
70 h
24 h
36
62
360
620
loading, several aliphatic and aromatic alkenes, including dienes
and internal olefins, were hydrogenated with full conversion (Taꢀ
ble 2, entries 3, 6, 9, 11, 13, and 17). A maximum TON of 25000
was observed for salꢀMOFꢀCo with 1ꢀoctene as the substrate. The
salꢀCoꢀMOF recovered from the dehydrogenation showed the
same PXRD pattern as the pristine salꢀMOF (Figure 1e), indicatꢀ
ing that the salꢀCoꢀMOF framework is also stable under the cataꢀ
lytic conditions.
COOMe
MeOOC
f
f
1
2
9
0
O
Fe
Co
70 h
72 h
64
0
640
0
e
We also prepared molecular (sal)Fe(THF) Cl species in order
x
O
to investigate the role of the framework in stabilizing the salꢀM
catalysts. Repeated synthetic attempts under a variety of condiꢀ
2
1
Fe
3 d
76
760
O
tions afforded
a tetrameric species with the formula of
Fe (sal) Cl (THF) as revealed by single crystal Xꢀray diffraction
4
4
4
2
a
Reaction conditions: 0.01 mol% salꢀFeꢀMOF or 0.003 mol% salꢀ
CoꢀMOF, 10 equiv NaBEt H (1.0 M in THF), alkene, THF, 40
(Figure 2a). Formation of such a tetranuclear complex is expected
3
as lowꢀcoordinationꢀnumber Fe species are not stable in solution
and can oligomerize through the Clꢀ or Oꢀbridging ligands. In
contrast, oligomerization is prohibited in salꢀMꢀMOFs due to
isolation of the metal sites. Importantly, Fe (sal) Cl (THF) was
b
ꢀ4
c
atm H , 23 °C. 6.5 × 10 mol% catalyst. 0.001 mol% catalyst.
.005 mol% catalyst. 0.05 mol% catalyst. 0.1 mol% catalyst.
2
d
e
f
0
4
4
4
2
Remarkably, at a 0.5 mol% catalyst loading, salꢀFeꢀMOF could
be recovered and reused for 1ꢀoctene hydrogenation at least 8
times without loss of catalytic activity (Figure 3) or MOF crystalꢀ
inactive towards olefin hydrogenation following the same treatꢀ
ment with 8 equiv. of NaBEt H, revealing the critical role of site
3
isolation for stabilizing the lowꢀcoordinate salꢀM catalysts.
3
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In summary, we have developed a novel postꢀsynthetic metaꢀ
9777.
(
(
2
(
17)Enthaler, S.; Haberberger, M.; Irran, E. Chem. Asian J. 2011, 6, 1613.
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lation strategy to discover MOFꢀsupported base metal catalysts
which do not possess homogeneous counterparts. The UiO MOF
bearing the Mꢀsalicylaldimine moiety (M = Fe and Co) are highly
active singleꢀsite solid catalysts for alkene hydrogenation, and can
be readily recycled and reused. This work thus shows that MOFs
provide a new platform for discovering base metal catalysts with
potential application in practical synthesis of fine chemicals.
(
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ASSOCIATED CONTENT
Supporting Information
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General experimental section; synthesis and characterization of
the ligand and MOFs; MOFꢀcatalyzed hydrogenation reactions;
MOF catalyst recycle and reuse procedures; EXAFS details and
fits; DFT calculation details. This material is available free of
charge via the Internet at http://pubs.acs.org.
Specht, C.; Gao, J.; Alivisatos, A. P.; Kruse, N.; Somorjai, G. A. Nano
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(
AUTHOR INFORMATION
(
2
Corresponding Author
wenbinlin@uchicago.edu
(29)Jagadeesh, R. V.; Surkus, A.ꢀE.; Junge, H.; Pohl, M.ꢀM.; Radnik, J.;
Rabeah, J.; Huan, H.; Schünemann, V.; Brückner, A.; Beller, M. Science
2013, 342, 1073.
Author Contributions
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2
30)Li, H.; Eddaoudi, M.; O'Keeffe, M.; Yaghi, O. M. Nature 1999, 402,
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†These authors contributed equally.
ACKNOWLEDGMENT
(
2
(
2
This work was supported by NSF (CHEꢀ1111490). We thank C.
Poon and K. Lu for experimental help. XAS analysis was perꢀ
formed at GeoSoilEnviroCARS, Advanced Photon Source (APS),
Argonne National Laboratory (ANL). GeoSoilEnviroCARS is
supported by the National Science Foundation (NSF) ꢀ Earth Sciꢀ
ences (EARꢀ1128799) and Department of Energy (DOE)ꢀ Geoꢀ
Sciences (DEꢀFG02ꢀ94ER14466). Single crystal diffraction
studies were performed at ChemMatCARS, APS, ANL.
ChemMatCARS is principally supported by the Divisions of
Chemistry (CHE) and Materials Research (DMR), NSF, under
grant number NSF/CHEꢀ1346572. Use of the Advanced Photon
Source, an Office of Science User Facility operated for the U.S.
DOE Office of Science by ANL, was supported by the U.S. DOE
under Contract No. DEꢀAC02ꢀ06CH11357.
(34)Della Rocca, J.; Liu, D.; Lin, W. Acc. Chem. Res. 2011, 44, 957.
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P.; Férey, G.; Morris, R. E.; Serre, C. Chem. Rev. 2012, 112, 1232.
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