Palladium Catalysis for Aerobic Oxidation Systems Using Robust Metal–Organic Framework

Article abstract of DOI:10.1002/anie.201909661

Described here is a new and viable approach to achieve Pd catalysis for aerobic oxidation systems (AOSs) by circumventing problems associated with both the oxidation and the catalysis through an all-in-one strategy, employing a robust metal–organic framework (MOF). The rational assembly of a Pd^II catalyst, phenanthroline ligand, and Cu^II species (electron-transfer mediator) into a MOF facilitates the fast regeneration of the Pd^II active species, through an enhanced electron transfer from in situ generated Pd⁰ to Cu^II, and then Cu^I to O₂, trapped in the framework, thus leading to a 10 times higher turnover number than that of the homogeneous counterpart for Pd-catalyzed desulfitative oxidative coupling reactions. Moreover, the MOF catalyst can be reused five times without losing activity. This work provides the first exploration of using a MOF as a promising platform for the development of Pd catalysis for AOSs with high efficiency, low catalyst loading, and reusability.

Full text of DOI:10.1002/anie.201909661

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201909661
German Edition: DOI: 10.1002/ange.201909661
Heterogeneous Catalysis
Hot Paper
Palladium Catalysis for Aerobic Oxidation Systems Using Robust
Metal–Organic Framework
Jiawei Li, Jianhua Liao, Yanwei Ren,* Chi Liu, Chenglong Yue, Jiaming Lu, and
Huanfeng Jiang*
Abstract: Described here is a new and viable approach to
achieve Pd catalysis for aerobic oxidation systems (AOSs) by
circumventing problems associated with both the oxidation
and the catalysis through an all-in-one strategy, employing
a robust metal–organic framework (MOF). The rational
assembly of a PdII catalyst, phenanthroline ligand, and CuII
species (electron-transfer mediator) into a MOF facilitates the
fast regeneration of the PdII active species, through an
enhanced electron transfer from in situ generated Pd0 to CuII,
and then CuI to O2, trapped in the framework, thus leading to
a 10 times higher turnover number than that of the homoge-
neous counterpart for Pd-catalyzed desulfitative oxidative
coupling reactions. Moreover, the MOF catalyst can be
reused five times without losing activity. This work provides
the first exploration of using a MOF as a promising platform
Scheme 1. a) Oxidation problem and b) catalysis problem in homoge-
for the development of Pd catalysis for AOSs with high
neous Pd catalysis for AOSs. c) MOFs based Pd catalysis system using
an all-in-one strategy.
efficiency, low catalyst loading, and reusability.
P
alladium-catalyzed aerobic oxidation reactions were the
focus of synthetic chemistry in recent years owing to their
crucial role for the synthesis of various valuable products.[1]
However, fast aggregation of the in situ generated Pd0 to Pd
black (deactivation), compared to the slow electron transfer
between Pd0 and molecular oxygen (O2) constitutes the
fundamental oxidation problem (Scheme 1a).[2] Extensive
endeavors for solving this problem focused on the addition of
electron-transfer mediators (ETMs) to carry the electron
from Pd0 to O2 along a low-energy pathway, thus boosting the
reoxidation of Pd0 to PdII.[3] Besides, considerable attention
has been centered on the development of ancillary ligands to
restrain the Pd0 aggregation.[4] In spite of the significant
progress offered by the above strategies (Scheme 1b), these
homogeneous Pd catalysis for aerobic oxidation systems
(AOSs) often suffer from problems (such as high PdII loading,
excess ETMs, and separation difficulties), which do not fulfill
the requirements for atom-economy.[5]
Metal–organic framework (MOF) based heterogeneous
catalysts have recently won a profound reputation because of
their well-defined structural features.[6] With precise knowl-
edge of Pd-catalyzed aerobic oxidations, the highly tunable
nature of MOFs enables the controllable immobilization of
a PdII catalyst, ligand, and ETM. Meanwhile, the site-isolation
nature and confinement effect of MOFs can stabilize the in
situ generated Pd0 and enhance the electron-transfer effi-
ciency. Moreover, MOFs can trap O2 in the pores, and thereby
create a local high-pressure O2 atmosphere around the
catalytic sites, thus further facilitating the efficient electron
transfer between Pd0, the ETM, and O2. Inspired by these
merits, we envisioned MOFs serving as a promising platform
for achieving advanced Pd-catalyzed AOSs through an all-in-
one strategy (Scheme 1c), thus solving the oxidation and
catalysis problems of Pd-catalyzed aerobic oxidations in an
efficient and sustainable manner. To the best of our knowl-
edge, it has never been reported.
As a proof-of-concept, the Pd-catalyzed desulfitative
oxidative coupling[7] between arenesulfinic acid salts and an
allylic alcohol was selected as a model reaction to verify the
MOF-based catalytic system because this reaction possesses
the representative oxidation and catalysis problems of Pd-
catalyzed AOSs. For example, the homogeneous system needs
a high loading of Pd(TFA)2(10 mol%) as the catalyst,
phenanthroline (phen; 20 mol%) as the ligand, and a stoi-
chiometric amount of Cu(TFA)2 as the ETM to achieve high
reactivity. Herein, we utilize a phen-containing linker, 1,10-
phenanthroline-3,8-dicarboxylic acid (PDC), as a difunctional
ligand to construct a zirconium-based MOF (UiO series),
[*] Dr. J. Li, Dr. Y. Ren, C. Liu, C. Yue, J. Lu, Prof. Dr. H. Jiang
Key Laboratory of Functional Molecular Engineering of Guangdong
Province, School of Chemistry and Chemical Engineering, South
China University of Technology
Guangzhou 510641(P. R. China)
E-mail: renyw@scut.edu.cn
jianghf@scut.edu.cn
Dr. J. Liao
School of Pharmaceutical Sciences, Gannan Medical University
Ganzhou 341000 (P. R. China)
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under:
https://doi.org/10.1002/anie.201909661.
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which can be metallized to achieve MOF-based Pd catalysis of
AOSs. The porous, stable, and tunable UiO MOFs have been
regarded as excellent carriers for heterogeneous catalysis.[8]
As shown in Scheme 2, solvothermal reaction of ZrCl4
and PDC afforded block nanoparticles (average size of about
30 nm), as confirmed by scanning-electron microscopy (SEM)
and transmission-electron microscopy (TEM) images (see
Figure S6 in the Supporting Information), termed UiO-67-
synthesized by varying the initial Pd(TFA)2/Cu(TFA)2 ratios.
The inductively coupled plasma mass spectrometry (ICP-MS)
analyses showed the molar ratios of Zr/Pd/Cu in the metalized
MOFs to be 6:2:0, 6:1.4:1.3, 6:1:2, 6:0.4:2.4, and 6:0:3.7,
respectively. PXRD patterns of these metallized MOFs
indicate the maintenance of their structural integrity (Fig-
ure 1a; see Figure S1). The reduced N2 adsorbed quantities,
BET areas, and pore sizes of the metallized MOFs can be
explained by the embedding of Pd and Cu salts into the
framework (Figures 1b,c). SEM and elemental mapping
images display uniform distribution of Zr, Pd, and Cu over
these metallized MOFs (see Figure S7).
To verify the valence state of the Pd and Cu species, and
their coordination modes in the metallized MOFs, X-ray
photoelectron spectroscopy (XPS) analyses were performed
(Figures 1d–f). The characteristic peaks of binding energies
(BEs) of Pd 3d5/2 at 338 eVand Pd 3d3/2 at 344 eV indicate the
oxidation state of Pd is + 2.[10] The divalent Cu state can be
inferred by the peaks of BEs located at 934 and 952 eV,
corresponding to Cu 2p3/2 and Cu 2p1/2, respectively, as well as
two typical satellite peaks at 940 and 945 eV.[11] The BE of N
1s in UiO-67-phen is 399 eV, which is attributed to the
nitrogen in phen, and is similar to that of 2,2’-bipyridine based
UiO-67-bpy.[12] In contrast, there are two N 1s peaks of BEs in
UiO-67-phen-Pd/Cu(1:0) and UiO-67-phen-Pd:Cu(0:1), sig-
nifying that the nitrogen atoms present two types of
coordination environments. One peak is analogous to UiO-
67-phen, and the other shifts toward a higher BE because of
a decrease in the electron density of the N atom by the
coordination between the N atoms in phen and PdII (or CuII)
ions. For UiO-67-phen-Pd/Cu(1:2), there are three types of N
1s peaks located at 400.5, 400 and 399 eV, implying the
coexistence of free phen, PdII-phen, and CuII-phen species.
These results clearly confirm the successful insertion of PdII
and CuII into UiO-67-phen, wherein the two cations coor-
dinate to phen with TFAÀ as a counterion as determined by
19F NMR data (Figure S8).
Scheme 2. Syntheses of metallized UiO-67-phen.
phen. The purity and crystallinity of UiO-67-phen were
confirmed by its PXRD pattern, which matches well with that
of UiO-67[9] (Figure 1a), suggesting they have the same
topological structure. UiO-67, comprising 12 connected
[Zr6O4(OH)4]12+ clusters and biphenyl-4,4’-dicarboxylate
(BPDC) ligands, contains two types of cages: an octahedral
cage and a tetrahedral cage, both of which are accessible by
equilateral triangle windows with side lengths of about
1.2 nm.[9] Because of the same molecular length of PDC and
BPDC, the pore structure of UiO-67-phen should be similar
to that of UiO-67. The Brunauer-Emmett-Teller (BET) area
of UiO-67-phen is calculated to be 1845 cm3 gÀ1 with a pore
width distribution centered at 1.1 nm according to the N2
adsorption isotherm at 77 K (Figures 1b,c). Thermal gravi-
metric analysis (TGA) reveals a thermal stability for UiO-67-
phen of up to 4508C (see Figure S2), guaranteeing its usage in
high-temperature reactions. The metallized analogues, UiO-
67-phen-Pd/Cu(x:y) [x:y = 1:0, 1:1, 1:2, 1:6, 0:1], were post-
To explore the catalytic performance of the metallized
UiO-67-phen, the desulfitative oxidative coupling reaction
between sodium benzenesul-
finate (1a) and but-3-en-2-ol
(2a) was selected. It turned
out the reaction proceeded
smoothly in the presence of
UiO-67-phen-Pd/Cu(1:6) at
optimal reaction conditions,
giving the desired b-aryl
ketone in excellent yield
(Table 1, entry 8). In contrast,
when reducing the amount of
CuII from 100 to 60 mol% in
the homogeneous system,
sharp deceases in yield could
be observed (entry 2). This
difference between homoge-
neous and MOF systems
became more remarkable as
Figure 1. a) PXRD patterns. b) N2 adsorption and desorption isotherms. c) Pore size distributions. d) XPS
spectra of the Pd 3d region. e) XPS spectra of the Cu 2p region. f) XPS spectra of the N 1s for UiO-67-phen
and metallized UiO-67-phen, respectively.
the amount of CuII further
reduced
to
20 mol%
2
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Table 1: Comparison of homogeneous and MOFs systems for the
desulfitative oxidative coupling reaction between 1a and 2a.[a]
conducted to prove the change of valence state of Cu and Pd
species (Figures 1d,e). The absence of two satellite peaks at
the copper 2p level and the presence of two new peaks (334
and 341 eV) at the palladium 3d level demonstrate that
[11]
almost all CuII has been converted into CuI
and that
a number of Pd species were in the reduced form.[14]
Entry Catalytic system
Yield[%][b] TON[c]
Decreasing the loading of UiO-67-phen-Pd/Cu(1:2) to
1 mol% (based on Pd) could also catalyze the reaction
without compromising the reactivity, leading to a 10 times
higher TON and 50 times less Cu consumption than
homogeneous counterparts (Table 1, entries 6 and 15). Fur-
ther lowering the catalyst loading to 0.2 mol% leads to
a TON of 230 (entry 16). The above findings indicate that the
PdII and ETM species in the framework display prominent
activities, especially at low catalyst/substrate ratio, probably
as a result of the confinement effect of the framework and/or
high surface utilization of MOF nanoparticles. Note that UiO-
67-phen-Pd/Cu(1:2) could be reused for at least five cycles
without apparent loss of activity (see Figure S10). ICP-MS of
the reaction filtrate showed negligible leaking of PdII and CuII
ions into the solution, confirming the heterogeneous nature of
this reaction. The PXRD pattern and N2 adsorption isotherm
of the recovered catalyst revealed that the porosity and
crystallinity were maintained after the catalysis (Figure 1a;
see Figure S3). XPS data imply that the oxidation states of Pd
and Cu remain at + 2 after the catalysis (Figures 1d,e), and
the TEM image showed no detectable Pd0 nanoparticles over
the framework (see Figure S9).
Next, the general applicability was examined, and a series
of different sodium arylsulfinates bearing electron-donating
and electron-withdrawing groups at the para-position were
found to be suitable substrates, producing the corresponding
b-aryl ketones in good to excellent yields (see Table S1, 3b–
e). Phenyl-substituted allyl alcohol was well tolerated to this
reaction, giving the desired product in moderate yield (see
Table S1, 3 f). An aliphatic allyl alcohol with an elongated
chain could also be converted into the corresponding product
in excellent yield (see Table S1, 3g). Besides, allyl primary
alcohol was found to be active, resulting in the formation of b-
aryl aldehyde in good yield (see Table S1, 3h).
Homogeneous system[d]
1[e]
2
3
4
5
Pd(TFA)2 [10 mol%]/Cu(TFA)2 [100 mol%] 80
8
Pd(TFA)2 [10 mol%]/Cu(TFA)2 [60 mol%]
Pd(TFA)2 [10 mol%]/Cu(TFA)2 [20 mol%]
Pd(TFA)2 [10 mol%]/Cu(TFA)2 [10 mol%]
Pd(TFA)2 [10 mol%]
52
20
11
6
5.2
2
1.1
0.6
4
6
Pd(TFA)2 [1 mol%]/Cu(TFA)2 [2 mol%]
4
MOFs system
7
UiO-67-phen (or no catalyst)
–
87
88
71
52
–
–
8
9
UiO-67-phen-Pd/Cu(1:6) [10 mol% Pd]
UiO-67-phen-Pd/Cu(1:2) [10 mol% Pd]
UiO-67-phen-Pd/Cu(1:1) [10 mol% Pd]
UiO-67-phen-Pd/Cu(1:0) [10 mol% Pd]
UiO-67-phen-Pd/Cu(0:1) [20 mol% Cu]
UiO-67-phen-Pd/Cu(1:2) [10 mol% Pd]
UiO-67-phen-Pd/Cu(1:2) [5 mol% Pd]
UiO-67-phen-Pd/Cu(1:2) [1 mol% Pd]
UiO-67-phen-Pd/Cu(1:2) [0.2 mol% Pd]
8.7
8.8
7.1
5.2
–
10
11
12
13[e]
14
15
16
38
86
89
46
3.8
17.2
89
230
[a] The reaction conditions were: 1a (0.5 mmol), 2a (2 mmol), O2
(1 atm), 1,4-dioxane (3 mL), 1008C and 20 h. [b] Determined by GC-MS
with n-dodecane as internal standard. [c] TON (turnover number): moles
of product per mole of catalyst used. [d] For homogeneous system, 4,7-
dimethyl-1,10-phenanthroline (20 mol%) was added. [e] Under anaero-
bic conditions.
(entries 3 and 9). As stoichiometric quantities or an excess
amount of the ETM are usually required to regenerate PdII in
homogeneous systems,[3b] the decreased ETM loading should
reduce the interaction between Pd0 and the ETM in solution,
leading to an unfavorable electron transfer and thus a dra-
matic decrease in activity. For the MOF system, the aggre-
gation of the in situ generated Pd0 should be prohibited by the
MOFs site isolation, and the fast electron transfer from Pd0 to
adjacent Cu2+ atoms should be achieved given their close
positioning within the confined pores of UiO-67-phen, even at
lower Cu2+ loadings. Although further reduction in the
amount of CuII to 10 mol% leads to slightly decreased yield
(entry 10), the MOF still outperforms the homogeneous
system.
Based on above results and previous reports,[7] we propose
a plausible mechanism of the Pd-catalyzed oxidative coupling
reaction within UiO-67-phen-Pd/Cu(1:2) (Scheme 3). The
aromatic sulfinic sodium is firstly coordinated to PdII in the
MOF with the extrusion of SO2. Then, the Heck-type
insertion of the allyl alcohol to the arylpalladium complex I
occurrs, affording the s-allkylpalladium complex II. The
selective b-hydride elimination of II gives the enol complex
III, which subsequently changes to IV with the transfer of
hydrogen to the a-carbon atom by spontaneous insertion of
2CuII-[MOF]-PdIIH. Either elimination of IV from the a-OH
or an anion-mediated reductive elimination is possible to
afford the final product, accompanied by the generation of
a Pd0 species. Different from a homogeneous system, the
efficient catalyst cycle was accomplished through the fast
electron transfer within the MOF. Initially, the in situ
generated Pd0 is prohibited from fast aggregation by the
MOFs catalytic site isolation. Subsequently, two electrons
transfer immediately from the generated Pd0 to adjacent CuII
When O2 (1 atm) was utilized as the sole oxidant, UiO-67-
phen-Pd/Cu(1:0) still gave
a moderate yield (Table 1,
entry 11), while only 6% yield could be observed for the
homogeneous system (entry 5). These findings distinctly
suggest a different behavior of O2 within MOF relative to
the homogeneous system. The entrapment of O2 within UiO-
67-phen-Pd/Cu(1:0) (see Figure S5) may form a local high-
pressure O2 atmosphere within the framework, thus enhanc-
ing the electron-transfer efficiency between O2 and Pd0, as
high-pressure O2 has been evidenced to increase the reox-
idation rate of Pd0 in homogeneous systems.[13] Additionally,
when UiO-67-phen-Pd/Cu(1:2) was utilized under anaerobic
conditions, an obviously reduced yield was observed
(entry 13). XPS investigation of this recovered catalyst was
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Conflict of interest
The authors declare no conflict of interest.
Keywords: aerobic oxidation · copper · heterogeneous catalysis ·
metal–organic framework · palladium
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Scheme 3. Proposed mechanism.
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a UiO MOF. This MOF-based catalyst exhibits markedly
increased TONs and largely reduced ETM consumption
compared to its homogeneous counterparts for Pd-catalyzed
desulfitative oxidative coupling reaction. Preorganization of
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Experimental Section
The experimental details included in the Supporting Information.
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Acknowledgements
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We are grateful for the financial support from the National
Key Research and Development Program of China
(2016YFA0602900) and the National Natural Science Foun-
dation of China (21420102003).
Manuscript received: August 3, 2019
Accepted manuscript online: September 5, 2019
Version of record online: && &&, &&&&
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Communications
Heterogeneous Catalysis
All-in-one: Immobilizing PdII and CuII
species into a robust metal–organic
framework (MOF) facilitates the Pd cat-
alysis for an aerobic oxidation system,
a desulfitative oxidative coupling reac-
tion, with high efficiency, low catalyst
loading, and reusability. These results
demonstrate the ability to merge a PdII
catalyst, a ligand, and an electron-transfer
mediator into a single MOF to boost
activity in an efficient and sustainable
manner.
J. Li, J. Liao, Y. Ren,* C. Liu, C. Yue, J. Lu,
H. Jiang*
&&&& — &&&&
Palladium Catalysis for Aerobic Oxidation
Systems Using Robust Metal–Organic
Framework
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