Multistep Engineering of Synergistic Catalysts in a Metal-Organic Framework for Tandem C-O Bond Cleavage

Article abstract of DOI:10.1021/jacs.0c00073

Cleavage of strong C-O bonds without breaking C-C/C-H bonds is a key step for catalytic conversion of renewable biomass to hydrocarbon feedstocks. Herein we report multistep sequential engineering of orthogonal Lewis acid and palladium nanoparticle (NP) catalysts in a metal-organic framework (MOF) built from (Al-OH)_n secondary building units and a mixture of 2,2′-bipyridine-5,5′-dicarboxylate (dcbpy) and 1,4-benzenediacrylate (pdac) ligands (1) for tandem C-O bond cleavage. Ozonolysis of 1 selectively removed pdac ligands to generate Al₂(OH)(OH₂) sites, which were subsequently triflated with trimethylsilyl triflate to afford strongly Lewis acidic sites for dehydroalkoxylation. Coordination of Pd(MeCN)₂Cl₂ to dcbpy ligands followed by in situ reduction produced orthogonal Pd NP sites in 1-OTf-Pd^NP as the hydrogenation catalyst. The selective and precise transformation of 1 into 1-OTf-Pd^NP was characterized step by step using powder X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, inductively coupled plasma mass spectrometry, infrared spectroscopy, and X-ray absorption spectroscopy. The hierarchical incorporation of orthogonal Lewis acid and Pd NP active sites endowed 1-OTf-Pd^NP with outstanding catalytic performance in apparent hydrogenolysis of etheric, alcoholic, and esteric C-O bonds to generate saturated alkanes via a tandem dehydroalkoxylation-hydrogenation process under relatively mild conditions. The reactivity of C-O bonds followed the trend of tertiary carbon > secondary carbon > primary carbon. Control experiments demonstrated the heterogeneous nature and recyclability of 1-OTf-Pd^NP and its superior catalytic activity over the homogeneous counterparts. Sequential engineering of multiple catalytic sites in MOFs thus presents a unique opportunity to address outstanding challenges in sustainable catalysis.

Full text of DOI:10.1021/jacs.0c00073

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Article
Multi-step Engineering of Synergistic Catalysts in a Metal-
Organic Framework for Tandem C-O Bond Cleavage
Yang Song, Xuanyu Feng, Justin S Chen, Carter Brzezinski, Ziwan Xu, and Wenbin Lin
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.0c00073 • Publication Date (Web): 20 Feb 2020
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Multi-step Engineering of Synergistic Catalysts in a Metal-Organic
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Yang Song, Xuanyu Feng, Justin S. Chen, Carter Brzezinski, Ziwan Xu, and Wenbin Lin*
th
Department of Chemistry, The University of Chicago, 929 East 57 Street, Chicago, IL 60637, USA
ABSTRACT: Cleavage of strong C-O bonds without breaking C-C/C-H bonds is a key step for catalytic conversion of renewable biomass
to hydrocarbon feedstocks. Herein we report multi-step sequential engineering of orthogonal Lewis acid and palladium nanoparticle (NP)
catalysts in a metal-organic framework (MOF) built from (Al-OH)
ylate(dcbpy) and 1,4-benzenediacrylate (pdac) ligands (1) for tandem C-O bond cleavage. Ozonolysis of 1 selectively removed pdac ligands
to generate Al (OH)(OH ) sites which were subsequently triflated with trimethyl triflate (Me SiOTf) to afford strongly Lewis acidic sites for
dehydroalkoxylation. Coordination of Pd(MeCN) Cl to dcbpy ligands followed by in situ reduction produced orthogonal Pd NP sites in 1-
n
secondary building units and a mixture of 2,2'-bipyridine-5,5'-dicarbox-
2
2
3
2
2
NP
NP
OTf-Pd as the hydrogenation catalyst. Selective and precise transformation of 1 into 1-OTf-Pd was characterized step-by-step using
powder X-ray diffraction, transmission electron microscopy, thermogravimetric analysis, inductively coupled plasma-mass spectrometry,
infrared spectroscopy, and X-ray absorption spectroscopy. Hierarchical incorporation of orthogonal Lewis acid and Pd NP active sites en-
NP
dowed 1-OTf-Pd outstanding catalytic performance in apparent hydrogenolysis of etheric, alcoholic, and esteric C-O bonds to generate
saturated alkanes via a tandem dehydroalkoxylation-hydrogenation process under relatively mild conditions. The reactivity of C-O bonds
followed the trend of tertiary carbon > secondary carbon > primary carbon. Control experiments demonstrated the heterogeneous nature and
NP
recyclability of 1-OTf-Pd and its superior catalytic activity over the homogeneous counterparts. Sequential engineering of multiple cata-
lytic sites in MOFs thus present a unique opportunity to address outstanding challenges in sustainable catalysis.
INTRODUCTION
which is a common problem for other multi-catalytic systems in-
volving homogeneous catalysts.
36-38
The conversion of abundant and renewable biomass into value-
added hydrocarbon feedstocks provides a potential sustainable so-
lution to an ever-increasing global need for commodity chemicals
Metal-organic frameworks (MOFs) have emerged as a versatile
and tunable porous material platform for the design of structurally
1
-3
and fuels. The key step of biomass conversion involves reducing
and functionally uniform solid catalysts over the past two dec-
4
-8
39-43
the oxygen content (~40%) without breaking C-C/C-H bonds. In
the presence of hydrogen, strong C-O bonds of alcohols, ethers, and
esters in abundant lignocellulosic biomass can be selectively
ades.
As catalytic functionalities can be incorporated into
4
4-47
MOFs via organic linker functionalization,
lytically active species in pores/channels,
transformation of metal-hydroxo/oxo nodes,
entrapment of cata-
and more recently,
4
8-52
9-13
53-56
cleaved in a hydrodeoxygenation process.
Development of
it is feasible to in-
novel catalytic technologies for efficient hydrodeoxygenation of C-
O bonds in biomass offers a viable pathway towards green, effi-
cient, and economic biomass utilization and establishing the bio-
stall multiple catalytic functionalities in MOFs via judicious com-
bination of metal/metal-oxo nodes and functional organic ligand
linkers followed by appropriate post-synthetic tranfromations.
5
7-63
1
4
renewable industry.
The rigid, periodic, and porous structures of MOFs isolate disparate
catalysts from each other, preventing their potential interference to
afford truly orthogonal catalytic sites. However, due to the diffi-
culty in characterizing MOFs after multistep functionalization, se-
quential engineering of multiple catalytic sites into MOFs has not
been realized. Herein we report the first attempt at multi-step syn-
thetic manipulations of an aluminum MOF to generate Lewis acid
catalysts and Pd NPs for tandem catalytic hydrodeoxygenation of
ethers, alcohols, and esters.
Among many strategies for the catalytic hydrodeoxygenation of
15-25
lignocellulosic biomass,
one-pot tandem catalysis offers an ef-
ficient method to break strong C-O bonds and transform biomass
2
6-29
into valuable hydrocarbon fuels.
In particular, Marks and
coworkers coupled tandem catalytic cycles of C-O dehydroalkox-
ylation and olefin hydrogenation to drive hydrogenolysis of ethers,
alcohols, and esters with a combination of homogeneous Lewis
3
0-34
acid catalysts and Pd nanoparticles (NPs).
Thermodynamic
analysis revealed that exothermic Pd NP-catalyzed hydrogenation
cycle could compensate endothermic acid-catalyzed C-O dehy-
In this work, we targeted a mixed-ligand MOF (1) built from (Al-
OH) secondary building units (SBUs) and a mixture of 2,2'-bipyr-
n
idine-5,5'-dicarboxylate(dcbpy) and 1,4-benzenediacrylate (pdac)
ligands to install both Lewis acid and Pd NP active sites via multi-
step synthetic manipulations (Scheme 1). The pdac ligands in 1
were selectively removed via post-synthetic ozonolysis to generate
3
0,
droalkoxylation cycle to render the overall reaction exothermic.
3
5
However, the effectiveness of this tandem catalytic hydrodeoxy-
genation process is limited by the reliance on non-reusable homog-
enous Lewis acid catalysts M(OTf) (M =Hf, Al, Zr, etc) and the
n
deactivation of metallic Pd NPs at elevated reaction temperatures.
The propensity for interference between homogeneous Lewis
Al
with trimethyl triflate (Me
sites for dehydroalkoxylation. Finally, coordination of
Pd(MeCN) Cl to dcbpy ligand followed by in situ reduction by
hydrogen produced orthogonal Pd NP sites as the hydrogenation
2
(OH)(OH
2
) sites. Subsequent triflation of Al
2 2
(OH)(OH ) sites
3
SiOTf) afforded strongly Lewis acidic
acidic M(OTf)
n
sites and Pd NPs adds another challenge to achiev-
ing long-term catalytic activities with truly orthogonal active sites,
2
2
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catalyst. In-depth characterization of the MOFs after each post-syn-
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thetic manipulation supported selective and precise transfor-
RESULTS AND DISCUSSION
NP
mations to install orthogonal active sites in 1-OTf-Pd . The pres-
NP
ence of both Lewis acid and Pd NP active sites in 1-OTf-Pd led
Synthesis of Mixed-Ligand MOF 1 and Removal of pdac Lig-
ands via Ozonolysis. The new MOF 1 with mixed dcbpy and pdac
ligands based on DUT-5 structure was synthesized solvothermally
to outstanding catalytic performance in apparent hydrogenolysis of
etheric, alcoholic, and esteric C-O bonds to generate alkanes via a
tandem dehydroalkoxylation-hydrogenation process under rela-
tively mild conditions. The reactivity of C-O bonds followed the
trend of tertiary carbon > secondary carbon > primary carbon. Con-
trol experiments confirmed the heterogeneous nature and recycla-
by heating a mixture of Al(NO
3 3 2
) ·9H O, dcbpy, pdac, and dime-
64-65
thylformamide (DMF) at 120 °C (Scheme S1, SI).
Powder X-
ray diffraction (PXRD) studies revealed that 1 was isostructural to
DUT-5 of the formula Al(OH)(bpdc) (bpdc = biphenyl-4,4’-dicar-
boxylate) and MOF-253 of the formula Al(OH)(dcbpy) (Figure 1c).
The formula of 1 was determined as Al(OH)(dcbpy)0.81(pdac)0.19
NP
bility of 1-OTf-Pd and its superior catalytic activity over the ho-
mogeneous counterparts.
0
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1
based on H NMR spectra of digested 1 (Figure S2, SI) and ther-
mogravimetric analysis (TGA) of 1 (Figure S3, SI). Scanning elec-
tron microscopy (SEM) and transmission electron microscopy
(TEM) imaging showed a plate-like morphology for 1 (Figure 1b,
6
4
e), similar to that of DUT-5.
2
N sorption measurements of 1
showed type I isotherms with a Brunauer-Emmett-Teller (BET)
2
2
surface area of 1499 m /g, comparable to that of DUT-5 (1613 m /g,
Figure 1d).
Ozonolysis pdac removal
1
Post-synthetic transformations have recently been used to fine-tune
micro- and meso-porosity of MOFs.
6
6-69
In particular, Maspoch and
coworkers used ozonolysis to remove olefin-containing ligands
from a mixed-ligand UiO-type MOF to afford both micro- and
6
9
meso-porosity. This ozonolysis process also removes some car-
boxylate ligands to generate Al (OH)(OH ) defect sites on the (Al-
OH) SBUs. We treated 1 with gaseous O (0.42 mol/h @ 6 L/min
flowing rate) to selectively remove the pdac ligands by cleaving
2
2
n
3
O
2
1-OH
the olefinic groups (Figure 1a, Scheme S2, SI). Further washing
with DMF/HCl (1M) (10:1 v:v) removed the residual organic frag-
Lewis acidity
enhancement
Triflation
2 2
ments trapped in the pores to afford 1-OH with Al (OH)(OH ) de-
1
fect sites as a white solid. H NMR of digested 1-OH revealed com-
plete removal of pdac ligands during ozonolysis (Figure S5, SI).
NMR and TGA analyses afforded a formula of Al(OH)(dcbpy)0.81-
2
(OH)0.38(H O)0.38 for 1-OH (Figure S6, SI). The crystallinity of 1
was maintained after ozonolysis as demonstrated by the similarity
of PXRD patterns between 1 and 1-OH (Figure 1c). TEM imaging
showed that 1-OH maintained the plate-like morphology of 1, with
evenly distributed spongy cleavages (Figure 1f). 1-OH showed a
1-OTf
Metalation Pd2+ coordination
2
BET surface area of 1190 m /g with the hysteresis characteristic of
mesoporosity (Figure 1d). The removal of pdac ligands slightly re-
duced the BET surface area but increased pore sizes in the 13 - 32
Å range (Figure S7, SI). Ozonolysis of 1 thus generated mesopores
which should facilitate substrate and product transport in catalytic
reactions.
1
-OTf-PdCl2
in situ Pd NP
Reduction
formation
1
-OTf-PdNP
Scheme 1. Schematic showing sequential engineering of Lewis
acid and Pd NP sites in 1.
2
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Journal of the American Chemical Society
a)
c)
b)
1
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2
00 nm
1
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e)
f)
d) 700
NP
1-OTf-Pd
after reaction)
(
600
1-OTf-PdCl2
500
400
300
200
100
0
1-OTf
1-OH
1 Adsorption
Desorption
1-OH Adsorption
1
1
(exp)
1-OH Desorption
DUT-5 (simu)
1
00 nm
100 nm
5
10
15
20
25
0.0
0.2
0.4
0.6
0.8
1.0
2q
Relative Pressure (P/P0)
Figure 1. (a) Chemical equation showing ozonolysis of 1 followed by washing with DMF/HCl (1 M) to afford 1-OH with Al
defect sites. (b) SEM image of as-synthesized 1. (c) The similarity of PXRD patterns of 1 (red), 1-OH (blue), 1-OTf (green), 1-OTf-PdCl
purple), and 1-OTf-Pd (khaki) to the simulated pattern of DUT-5 (black) indicates the crystallinity of the MOF was maintained after
multi-step post-synthetic manipulations. (d) N
2
(OH)(OH
2
)
2
NP
(
2
sorption isotherms of 1 (black) and 1-OH (blue). (e, f) TEM images of 1 (e) and 1-OH (f).
(E) between the x* and y* orbitals.78 1-OTf bound O
ited a g of 2.032, which corresponds to a E of 0.94 eV (Figure

Triflation of 1-OH and Lewis Acidity Determination for 1-OTf.
Although MOF nodes have been widely used as Lewis acidic sites
to catalyze organic transformations,
nificantly lower than the homogeneous benchmark Sc(OTf)
recently developed a triflation strategy to significantly enhance
2
exhib-
zz
7
0-73
their Lewis acidity is sig-
S13a, SI). In comparison, 1-OH displayed a gzz of 2.0352 with a
corresponding E of 0.85 eV. The 0.09 eV increase in E makes
1-OTf a much stronger Lewis acid and affords a more effective
catalyst for C-O bond cleavage. Free NMA has an emission max-
imum (max) at 433 nm when excited at 413 nm. Upon coordination
to 1-OTf, the Lewis acid adduct of NMA displayed a max at 470
nm (Figure 2c, Figure S14, SI). The energy shift of NMA emission
3
. We
7
4
Lewis acidity of MOF nodes. 1-OH was activated with Me
in benzene at room temperature for 12 h to afford 1-OTf as a pale-
yellow solid (Figure 2a). Me SiOTf quantitatively transformed
( -OTf) sites due to the oxophilic
Si groups. H NMR spectroscopy showed the gener-
Si) O w.r.t. the Al (OH)(OH ) sites
Figure S8, SI), agreeing well with the expected value of 2 for the
3
SiOTf
3
Al
2
(OH)(OH
2
) moieties to Al
2
2
1
nature of Me
3
was previously established to be linearly related to the Lewis acid-
ation of 1.93 equiv. of (Me
3
2
2
2
77, 79
ity of metal centers.
Using the reported empirical equation, we
(
calculated the E value of 1-OTf to be 0.93 eV, which is almost
identical to the value measured by superoxide EPR spectroscopy.
In comparison, 1-OH only shifted the max of NMA emission to 463
nm, with a calculated E of 0.84 eV. Triflation of Al (OH)(OH )
2 2
moieties thus significantly enhanced Lewis acidity of 1-OTf for
proposed activation process (Scheme S3, SI). Diffuse reflectance
infrared Fourier transform spectroscopy (DRIFTS) supported the
removal of Al
2 2
(OH)(OH ) moieties. The increased absorption at
-1
OTf
1
231 – 1266 cm in 1-OTf corresponded to the ν(S=O ) band
Figure 2b, Figure S9a, SI). The sharp stretching band at 3708 cm-
(
catalytic applications.
1
75
was observed for bridging 
but this band shifted significantly to 3687 cm for 1-OTf (Figure
b, Figure S9b, SI). Electron-withdrawing OTf groups weaken the
-OH groups in 1-OTf, leading to a shift to lower
2
-OH groups in both 1 and 1-OH,
-1
2
O-H bonds of 
2
-1
energy. The broad peak centered at 3689 cm in 1-OH was at-
tributed to hydrogen bonding interactions between neighboring Al-
OH and Al-OH moieties.
2
76
We quantified Lewis acidity enhancement in 1-OTf by electron
paramagnetic resonance (EPR) spectroscopy of MOF-bound super-
oxide (O
methylacridone (NMA).
generated in situ by the 1e reduction of O

2
) and fluorescence spectroscopy of MOF-bound N-
7
4, 77

2
Superoxide radical ions (O
) can be

2
, which readily bind to
Lewis acidic Al centers by displacing the weakly coordinating tri-

2
) species (Figure S13b, SI).
flate groups to form EPR-active Al(O
Coordination to Lewis acids significantly shifted the EPR signal of

2
, especially the gzz tensor that is determined by energy splitting
O
3
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of 27.8% (expected 28.6%) after ramping the temperature to 800
°C (Figure S11, SI). TEM imaging showed that 1-OTf-PdCl main-
tained the plate-like morphology of 1 (Figure S10, SI), whereas
PXRD studies indicated that 1-OTf-PdCl maintained crystalline
structure of 1 (Figure 1c). Pd coordination environment of 1-OTf-
PdCl was studied by extended X-ray absorption fine structure
EXAFS) spectroscopy. The EXAFS data was collected at Pd K-
edge and fitted with reported crystal structure of (bpy)PdCl (Fig-
was
well fit with the structure to afford nearly identical coordination
geometry and bond lengths (Figure 3d). Specifically, the Pd centers
2
in 1-OTf-PdCl coordinate to two chlorides and one bpy ligand in
a near square planar geometry with an average Pd-N bond length
of 2.04 ± 0.01 Å and an average Pd-Cl bond length of 2.30 ± 0.02
Å (Table S1, SI). X-ray absorption near edge structure (XANES)
a)
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
2
2
2
(
2
8
0
ure 3b). The EXAFS feature of Pd centers in 1-OTf-PdCl
2
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
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7
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0
1
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0
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0
1
2
3
4
5
6
7
8
9
0
b)
c)
1
1
4
70 nm
-OH
1-OTf
2
spectroscopy showed that the Pd centers in 1-OTf-PdCl adopt +2
oxidation state (Figure S12).
4
33 nm
463 nm
3708 cm-1
II
Upon treatment with H
2
in the catalytic reaction, the Pd centers in
NMA only
1-OH
1-OTf-PdCl were readily reduced to form metallic Pd NPs in 1-
2
NP
3
687 cm
-
1
1-OTf
OTf-Pd . To investigate the true catalytic active species during the
reaction process, we characterized the MOF materials recovered
from catalytic C-O cleavage reactions by PXRD, TEM, and
XANES. PXRD studies showed that the MOF after catalysis re-
mained crystalline (Figure 1c), whereas TEM imaging indicated
the formation of Pd NPs which were dispersed evenly in the MOF
4000
3500
3000
2500
2000
1500
1000
400
420
440
460
480
500
Wavenumber (cm-1
)
Wavelength (nm)
Figure 2. (a) Chemical equation showing triflation of 1-OH to af-
ford 1-OTf. (b) DRIFT spectra of 1 (blue), 1-OH (red), and 1-OTf
(black) show a significant shift of ν( -OH) from 3708 cm (1,
2
blue, and 1-OH, red) to 3687 cm (1-OTf, black). (c) Fluorescence
spectra of 1-OTf (black), 1-OH (red), and free NMA (dashed).
-1
0
-
1
matrix (Figure 3c). We further characterized the Pd species in the
recovered MOF by XANES. The recovered MOF showed XANES
0
II
features corresponding to both Pd and Pd species. We fitted the
NP
XANES spectra of 1-OTf-Pd with a linear combination of
XANES spectra of PdCl and Pd foil. The fitting gave ~48% Pd
2
Synthesis and Characterization of 1-OTf-PdCl
2
and 1-OTf-
Cl in THF to
0
NP
Pd . 1-OTf was further metalated with Pd(MeCN)
2
2
species in the recovered MOF (Figure 3e); it is likely that surface
afford the pre-catalyst 1-OTf-PdCl
ductively coupled plasma-mass spectrometry (ICP-MS) indicated
an Al/Pd ratio of 2.10, corresponding to formula of
Al(OH)(dcbpy)0.81(PdCl 0.48(OTf)0.38 for 1-OTf-PdCl . This for-
2
(Figure 3a, Scheme S4, SI). In-
NP
II
Pd centers of 1-OTf-Pd were oxidized by air to afford Pd species
when the samples were processed for XANES studies.
a
2
)
2
mula was supported by TGA analysis, which gave a residual weight
a)
b)
c)
d)10
e)1.5
exp
fit
window
Nbpy
1.2
8
6
4
2
0
Cl
bpy
C
1
bpy
2
0.9
C
Nbpy + C
Nbpy + C
bpy
bpy
1
2
0.6
0.3
0.0
exp
fit
Pd foil
PdCl2
50 nm
-0.3
0
1
2
3
4
24340
24360
24380
24400
R(Å)
Energy (eV)
Figure 3. (a) Chemical equation showing metalation of 1-OTf with Pd(MeCN)
2
Cl
2 2
to afford 1-OTf-PdCl and in situ reduction of 1-OTf-
NP
PdCl
2
to generate 1-OTf-Pd . (b) Fragment structure of (bpy)PdCl
2
for EXAFS fitting of the Pd coordination environment in 1-OTf-PdCl .
2
NP
H atoms were omitted for clarity. (c) TEM image of 1-OTf-Pd shows evenly distributed Pd NPs in the MOF matrix after in situ reduction
4
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Journal of the American Chemical Society
2
in catalytic reactions. (d) EXAFS spectrum (gray solid line) and fit (black circles) in R-space at the Pd K-edge adsorption of 1-OTf-PdCl .
NP
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
2
(e) Linear combination fitting of 1-OTf-Pd XANES feature using those of Pd foil and PdCl as the basis functions.
to effect such a tandem process.90-94 In particular, metal triflate salts
and supported Pd catalysts effectively catalyzed ether and alcohol
C-O bond hydrogenolysis to generate saturated hydrocarbons in a
1
2
-OTf-PdCl Catalyzed Tandem Ether/alcohol C-O Bond
Cleavage. Etheric and alcoholic C-O linkages widely exist in bio-
mass-based feedstocks. Their strong bonds present a major chal-
lenge for converting biomass into chemicals and hydrocarbon fuels
Acids are shown to catalyze the
C-O bond formation from hydroalkoxylation between alcohols and
as well as its reversible process, dehydroalkoxyla-
tion to cleave an alkyl ether to form an olefin and an alcohol.
As the dehydroalkoxylation process is endothermic with ΔH ≈
10~20 kcal/mol, its coupling with an exothermic alkene hydro-
genation reaction makes the overall C-O bond cleavage reaction
exothermic and produces a saturated alkane and an alcohol as the
Multiple catalyst systems containing acid catalysts,
such as homogeneous mineral acids and Lewis acids or heteroge-
neous acidic materials, and hydrogenation catalysts have been used
30-31, 34
tandem manner.
tivate, require harsh conditions with elevated reaction temperatures
and high H pressures, and produce undesirable dimerized or aro-
matized byproducts. With isolated catalytic sites confined by the
These catalyst systems tend to rapidly deac-
1
2, 34, 81-85
with low oxygen contents.
2
7
4, 86-88
alkenes
30-31,
NP
MOF framework, in situ generated 1-OTf-Pd catalyst is expected
to significantly stabilize strongly Lewis acidic Al ( -OTf) sites
3
5
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
2
2
and evenly distributed Pd NPs to realize highly effective tandem
catalysis. At the same time, the pore restriction in the 1D channels
NP
of 1-OTf-Pd can prevent undesired dimerization and aromatiza-
tion to improve product selectivity.
3
0, 89
products.
Table 1. Screening of reaction conditions for 1-OTf-PdCl
2
Catalyzed Tandem Etheric/Alcohol C-O Bond Cleavagea
Entry
Catalyst (mol % Loading)
Solvent
Temp./ oC
Yield of menthane / %
TON
1
2
3
4
5
6
1-OTf-PdCl
1-OTf-PdCl
1-OTf-PdCl
1-OTf-PdCl
1-OTf-PdCl
-
2
2
2
2
2
(0.5%)
(0.5%)
(0.1%)
(0.2%)
(0.1%)
Octane
THF
neat
130
130
130
100
100
100
100
100
100
100
74
31
40
>99
80
N.D.
<1
22
9
148
62
400
>500
800
-
1,2-dichloroethane
1,2-dichloroethane
1,2-dichloroethane
1,2-dichloroethane
1,2-dichloroethane
1,2-dichloroethane
1,2-dichloroethane
b
7
8
1-OTf (0.2 %)
-
c
1-OH-PdCl
2
(0.2 %)
+ Pd (0.2 %)
HOTf + Pd (0.2 %)
110
45
15
d
9
Al(OTf)
3
1
0e
3
a
Reaction conditions: 1-OTf-PdCl (loading w.r.t. Al
determined by GC-MS analysis. Catalysts: 0.2 mol% of 1-OTf. Catalysts: 0.2 mol% of 1-OH-PdCl
+ 0.25 mol% Pd(MeCN) Cl . Catalysts: 0.2 mol% of HOTf + 0.25 mol% Pd(MeCN) Cl .
2 2 2 2
2
2
(
2
-OTf), 0.6 mmol 1,8-cineole, 20 bar H
2
, 1 mL solvent or neat condition, 24 h; Yield of menthane was
b
c
d
2
(w.r.t. Al
2
(OH)(OH
2
)). Catalysts: 0.2 mol% of Al(OTf)
3
e
1
,8-cinole was used as a model compound to optimize the reaction
10). These results suggest that C-O bond cleavage by 1-OTf-PdCl
occurs in a tandem manner, where strong Lewis acidic Al (
2
conditions for tandem C-O bond cleavage (Table 1). Initial screen-
ing of solvents revealed that 1,8-cinole could be quantitatively con-
verted to menthane in 1,2-dichloroethane at 0.2 mol% loading of
2
2
-OTf)
sites on the SBUs catalyze the dehydroalkoxylation of etheric/al-
coholic C-O bonds to afford C=C bonds which are hydrogenated
by nearby Pd NPs confined in the MOF channels. The hydrogena-
tion reaction pushes the equilibrium to the right to form saturated
hydrocarbons (Figure 4a).
1-OTf-PdCl
der 20 bar of H
2
[w.r.t. Lewis acidic Al
2
2
( -OTf) sites] and 100 °C un-
for 24 h. Nonpolar solvents such as octane and
2
coordinating solvents such as THF gave lower catalytic perfor-
mance, likely due to poor substrate solubility and poisoning of
Lewis acidic metal sites, respectively. The highest TON of 800 was
obtained when the catalyst loading was lowered to 0.1 mol%; this
level of catalytic activity significantly outperformed previously re-
is also advantageous to the
well-studied homogeneous metal triflate plus supported Pd NP sys-
tem by avoiding the use of substoichiometric amounts of expensive
2
We next examined the substrate scope of 1-OTf-PdCl catalyzed
tandem etheric/alcoholic C-O bond cleavage. A broad scope of sub-
strates including tertiary (3°), secondary (2°), and primary (1°) al-
ported catalytic systems. 1-OTf-PdCl
2
cohols/ethers were readily converted to alkanes by 1-OTf-PdCl
2
under similar conditions (Table 2). Quantitative conversion of 3°
alcohol (1-methylcyclohexanol) and 3° ether (1,8-cineole) to satu-
rated alkanes was achieved at 0.1-0.2 mol% loading of 1-OTf-
4 3 3
metal triflates such as Hf(OTf) , Sc(OTf) , and Yb(OTf) .
2
PdCl and at 100 °C (Table 2, entries 1 and 2). Reaction tempera-
Several control experiments were conducted to gain insights into
the tandem catalytic pathway of 1-OTf-PdCl mediated C-O bond
tures as high as 150 °C were needed to quantitatively convert 2°
alcohols and ethers (cyclohexanol, 2-octanol, dicyclohexyl ether,
and cyclohexyl phenyl ether) to corresponding saturated alkanes
(Table 2, entries 4-7). 1° alcohol (1-heptanol) required even higher
reaction temperatures of up to 200 °C and 0.5 mol% loading of 1-
2
cleavage. In the absence of the MOF catalyst, 1,8-cinole was totally
unreactive under the reaction condition (Table 1, entry 6). At a
loading of 0.2 mol% 1-OTf, a negligible amount of menthane was
detected (Table 1, entry 7). The lack of activity of 1-OTf is likely
due to the unfavorable thermodynamics of the dehydroalkoxylation
OTf-PdCl
product selectivity was observed for different kinds of substrates
with 1-OTf-PdCl as the catalyst without detection of any unde-
sired dimerization or aromatization product. The outstanding prod-
uct selectivity of 1-OTf-PdCl is attributed to the pore size exclu-
2
to afford heptane in 92% yield (Table 2, entry 8). High
reaction. 0.2 mol% loading of 1-OH-PdCl
menthane yield of 22% (Table 1, entry 8), consistent with much
lower Lewis acidity of Al (OH)(OH ) sites than Al ( -OTf) sites.
Under identical conditions, homogenous controls with Al(OTf)
plus Pd(MeCN) Cl and HOTf plus Pd(MeCN) Cl gave very low
menthane yields of 9% and 3%, respectvely (Table 1, entries 9 and
2
gave a much lower
2
2
2
2
2
2
3
sion by the uniform MOF channels and well-defined, site-isolated
Lewis acids and Pd NPs in the MOF. Notably, 1° ethers with active
2
2
2
2
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Page 6 of 11
β-hydrogen atoms, i.e., phenethoxybenzene and (2-methoxy-
ethyl)benzene, underwent C-O bond cleavage at 150 °C and 130
C, respectively, to produce ethylbenzene as the main product with
a high selectivity over the over-hydrogenated product methylcyclo-
hexane.
a)
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
°
Table 2. Substrate Scope for 1-OTf-PdCl
Etheric/Alcoholic C-O Bond Cleavage
2
Catalyzed Tandem
a
b)
100
Catalyst
Loading Temperature
Reaction
Conversion
Product
Entry
1
Substrate
(Yield)
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
0.1 mol%
0.2 mol%
0.1 mol%
0.1 mol%
0.1 mol%
0.1 mol%
0.2 mol%
0.5 mol%
0.2 mol%
0.2 mol%
100 °C
100 °C
100 °C
150 °C
150 °C
150 °C
150 °C
200 °C
150 °C
130 °C
100% (>99%)
100% (>99%)
80% (80%)
80
60
40
20
0
2
3
4
5
6
7
8
9
100% (>99%)
100% (97%)
1
2
3
4
5
6
94% (89%)b
Recycle Run
Figure 4. (a) Proposed tandem pathway for 1-OTf-PdCl
C-O bond cleavage. (b) Recycle experiments for 1-OTf-PdCl
alyzed C-O bond cleavage of 1-methylcyclohexanol. Plots of
methylcyclohexane yields (%) in six consecutive runs with 3 h of
reaction time.
2
-mediated
cat-
100% (>99%)
100% (92%)
100% (89%)b
70% (61%)b
2
10
2
1-OTf-PdCl Catalyzed Tandem Ester C-O Bond Cleavage. Es-
ter groups also widely exist in bio-derived molecules such as tri-
glycerides, fats, and oils, which provide a source of renewable die-
sel after their decarboxylation.
methods require high temperatures of up to 500 °C to thermally
crack the C-O bond followed by CO
plus Pd/C have recently been used to catalyze tandem ester C-O
bond cleavage with moderate to good selectivity and yields.
a
Unless noted, all reactions performed with indicated amount of 1-OTf-
PdCl , 0.6 mmol of substrate, and 20 bar H in 1.0 mL of 1,2-dichloroethane
95-97
Traditional decarboxylation
2
2
for 24 h. Conversions and yields determined by GC-MS integrals with me-
9
8-101
sitylene as the internal standard. See Table S4, SI for details and isolated
2
release.
Metal triflates
b
yields for select products. Reaction performed in 1 bar H
2
.
3
2-33, 102
Several lines of evidence support the heterogeneity of 1-OTf-PdCl
2
in tandem C-O bond cleavage reactions. The catalysts recovered
from C-O bond cleavage reactions exhibited identical PXRD pat-
terns to pristine 1, indicating structural stability of 1-OTf-PdCl in
2
catalytic reactions (Figure 1c). Lewis acidity quantification on the
MOF recovered from the catalytic reaction confirmed the mainte-
nance of Lewis acidity in the catalytic process (Figure S15, SI).
1-OTf-PdCl was also proved highly active for tandem ester C-O
bond cleavage with a reactivity trend of 3° carbon > 2° carbon > 1°
carbon (Table 3). The 3° ester terpinyl acetate was effectively
cleaved to produce menthane at 0.2 mol% loading of 1-OTf-PdCl
2
at 100 °C, affording a TON of 440 (Table 3, entry 1). The 2° ester
L-menthyl acetate was decarboxylated in the presence of 0.5 mol%
2
ICP-MS analysis showed minimal leaching of Al (0.6%) and Pd
2
1-OTf-PdCl at 150 °C to afford menthane in quantitative yield
19
(0.02%) into the supernatant after the first reaction run whereas
F
(Table 3, entry 2). Other 2° acetate or propionate esters, i.e., cyclo-
hexyl acetate, and cyclohexyl propionate, readily underwent C-O
2
NMR analysis indicated negligible leaching of OTf into the super-
natant after catalysis (Figure S19, SI). “Hot filtration” test was also
carried out to further exclude the possibility of soluble metal or acid
species contributing to the catalytic performance (Figure S18, SI).
After the reaction was interrupted, the solution phase and the solid
phase were separated and used, respectively, for another reaction
run. The recovered solid retained the catalytic activity but the solu-
cleavage at 0.5 mol% 1-OTf-PdCl at 150 °C to afford decarbox-
ylated products in 62 to 84% yields (Table 3, entries 4-5). For the
1° ester octyl acetate, a higher temperate of 200 °C was needed to
afford octane in 79% yield (Table 3, entry 6). Interestingly, 1° ester
with active -hydrogen atoms, i.e., phenethyl acetate, readily un-
2
derwent C-O cleavage at 0.2 mol% loading of 1-OTf-PdCl and
tion was totally inactive, proving the heterogeneity of 1-OTf-PdCl
Impressively, 1-OTf-PdCl was readily recovered by simple cen-
trifugation and reused for at least 5 times without significant drop
in catalytic activity (Figure 4b). Moreover, 1-OTf-PdCl catalyzed
2
.
1
30 °C to afford ethylbenzene in 94% yield (Table 3, entry 7).
2
Moreover, the lactone·5-hexanolide also underwent tandem C-O
cleavage to generate the saturated carboxylic acid (hexanoic acid)
in 61% yield (Table 3, entry 8). Such a MOF-based tandem catalyst
system thus provided a potent solution for cleavage of esteric C-O
bonds.
2
tandem C-O cleavage of 1,8-cinole at ~2 g scale (20 times larger
scale) afforded menthane in 75% yield in 24 h under standard re-
action conditions. The excellent thermal stability and recyclability
make 1-OTf-PdCl
2
a potential candidate catalyst for practical tan-
dem etheric/alcoholic C-O bond cleavage.
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Journal of the American Chemical Society
Table 3. Substrate Scope for 1-OTf-PdCl
Bond Cleavage
2
Catalyzed Ester C-O
ACKNOWLEDGMENT
a
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
This work was supported by NSF (CHE-1464941) and the Univer-
sity of Chicago. We thank Mr. Xiaomin Jiang and Mr. Taokun Luo
for experimental help. We thank Mr. Lingbowei Hu and Dr. Viresh
Rawal for the help with ozonolysis. XAS analysis was performed
at Beamline 10-BM, supported by the Materials Research Collab-
orative Access Team (MRCAT). 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. DE-AC02-06CH11357.
Catalyst
Loading Temperature
Reaction
Conversion
Product
Entry
1
Substrate
(Yield)
0.2 mol%
100 °C
100% (88%)b
2
3
4
5
0.5 mol%
0.1 mol%
0.5 mol%
0.5 mol%
150 °C
150 °C
150 °C
150 °C
100% (>99%)
45% (45%)
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
91% (84%)b
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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
Synergistic Lewis acidic and metallic Pd sites in a MOF
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1
ACS Paragon Plus Environment