Biomimetic Activation of Molecular Oxygen with a Combined Metalloporphyrinic Framework and Co-catalyst Platform

Article abstract of DOI:10.1002/cctc.201601606

Cytochromes P450 are powerful biocatalysts that present high catalytic efficiency in the aerobic oxidation of hydrocarbons under mild conditions. Even though metal–organic frameworks (MOFs), consisting of biomimetic metalloporphyrin moieties, are highly active in a number of reactions, they are almost powerless in the aerobic oxidation of inert hydrocarbons under mild conditions. Inspired by the catalytic mechanism of enzymes, we introduce N-hydroxyphthalimide (NHPI) as an assistant catalyst to help metalloporphyrinic MOF catalysis, for which NHPI acts as a proton- and electron-transfer mediator. The coupled biomimetic system is efficient in the aerobic oxidation of arylalkanes under mild conditions. The catalytic efficiency is significantly improved if the [WZn{Co(H₂O)}₂(ZnW₉O₃₄)₂]^12? polyoxometalate is used as a co-catalyst. The biomimetic platform exhibits enzyme-like characters by imitating the structural features, active sites, and catalytic mechanism of enzymes.

Full text of DOI:10.1002/cctc.201601606

Accepted Article
Title: Biomimetic Activation of Molecular Oxygen with a Combined
Metalloporphyrinic Framework and Co-catalyst Platform
Authors: Chuan-De Wu and min Zhao
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Link to VoR: http://dx.doi.org/10.1002/cctc.201601606
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Biomimetic Activation of Molecular Oxygen with a Combined
Metalloporphyrinic Framework and Co-catalyst Platform
Min Zhao and Chuan-De Wu*
Abstract: Cytochromes P450 are powerful biocatalysts which
present high catalytic efficiency on the aerobic oxidation of
hydrocarbons under mild conditions. Even though metal-organic
frameworks (MOFs), consisting of biomimetic metalloporphyrin
moieties, are highly active on a number of reactions, however, they
are almost powerless on the aerobic oxidation of inert hydrocarbons
under mild conditions. Inspired by the catalytic mechanism of
enzymes, we introduce N-hydroxyphthalimide (NHPI) as an assistant
catalyst to help metalloporphyrinic MOF catalysis, in which NHPI
acts as a proton- and electron-transfer mediator. The coupled
biomimetic system is efficient on the aerobic oxidation of arylalkanes
under mild conditions. The catalytic efficiency is significantly
improved when polyoxometallate, [WZn{Co(H2O)}2(ZnW9O34)2]12−, is
used as a co-catalyst. The biomimetic platform exhibits enzyme-like
characters by imitating the structural features, active sites and
catalytic mechanism of enzymes.
biomimetic metalloporphyrin moieties onto porous solid supports
has been developed to improve the catalytic efficiency and
sustainability. To tune the pore structures and modify the
functional groups of metal-organic frameworks (MOFs), the
emerging porous materials have been extensively explored as
the very promising materials for applications in various fields.5,6
In term of catalytic application, MOFs with the super characters
of high porosity, high surface areas, and tunable hydrophobic
and hydrophilic pore nature have been used as host matrices to
immobilize molecular catalysts.6 Immobilization of molecular
catalysts onto the pore surfaces of MOF materials can facilitate
the recognition, transportation and enrichment of substrate
molecules to contact with catalytic sites, and provide
collaborative microenvironment to synergistically improve the
catalytic efficiency. These features of MOFs are similar to those
of enzymes when biomimetic metalloporphyrin moieties are
immobilized onto the pore surfaces.7 Compared with those of
molecular metalloporphyrins, the catalytic efficiency, selectivity
and sustainability of biomimetic MOFs are significantly
improved.7,8 However, the catalytic properties of these
biomimetic MOFs remain much inferior to those of enzymes,
because metalloporphyrinic MOFs are almost inactive on direct
activation of molecular oxygen for the inert C-H bond
oxygenation under mild conditions.
Enzymes are a class of powerful biocatalysts, which can prompt
numerous reactions with unmatched efficiency and selectivity
under mild conditions.1 The most intriguing character of
enzymatic catalysis lies in the fact that some chemical
transformations cannot be easily realized by traditional catalysts.
For example, activation of molecular oxygen by traditional
catalysts often performed under harsh reaction conditions (high
temperature and pressure) or in the presence of sacrificial
agents (e.g. aldehydes) with low conversion and selectivity,
whereas the aerobic oxidation of unactivated hydrocarbons can
be easily realized under mild conditions (room temperature and
atmosphere pressure) by cytochromes P450 (P450).2,3
Accordingly, biomimetic catalysis has been a great attractive
and promising field for highly efficient catalysis. Attracted by the
unique catalytic properties of P450, numerous porphyrins and
metalloporphyrins have been developed to mimic the prosthetic
groups of the native enzymes for biomimetic catalysis.4 The
biomimetic metalloporphyrins exhibit high catalytic efficiency in
numerous reactions. The major issues to obstruct their practical
applications lie in their easy deactivation nature and inability on
activation of molecular oxygen for the oxidation of unactivated
hydrocarbons under mild conditions.
In fact, in the biocatalyst system, activation of molecular
oxygen for the aerobic oxidation of unactivated hydrocarbons is
the synergistic work of prosthetic groups and coenzymes, such
as reductases. In the aerobic oxidation cycle, the reductase
reduces one oxygen to form a water molecule, whereas the
metalloporphyrin inserts an oxygen atom into the unactivated
hydrocarbon through
a hydrogen abstraction and oxygen
rebound mechanism.9 Compared with the biological system, the
inability of metalloporphyrinic MOFs on direct activation of
molecular oxygen should be ascribed to the lack of assistant
catalysts by donating the necessary electrons. As demonstrated
in the text, the porous metalloporphyrinic framework
[Cu4(H2O)4(Cu-L)]·4DMF·7[(CH3)2NH2]NO3·26H2O (CZJ-6, CZJ
= Chemistry Department of Zhejiang University), building from
four-connected paddle-wheel [Cu2(COO)4(H2O)2] secondary
building units (SBUs) and eight-branched metalloporphyrin
Inspired by heme molecules in protein scaffolds which not
only can sustain high efficiency for numerous catalytic cycles but
also exhibit super activity on the aerobic oxidation of inert
substrates under mild conditions, immobilization of the
ligands,
Cu-L
(H10L
=
5,10,15,20-tetrakis-(3,5-
dicarboxyphenyl)porphine; Scheme S1), is inactive on the
aerobic oxidation of arylalkanes under mild conditions. It is
interesting that the aerobic oxidation reaction can be easily
prompted when N-hydroxyphthalimide (NHPI) was used as an
assistant catalyst. Moreover, the catalytic efficiency can be
significantly improved when a co-catalyst polyoxometallate
(POM), [WZn{Co(H2O)}2(ZnW9O34)2]12−, was introduced into the
catalytic system. The biomimetic platform is highly efficient and
selective on the aerobic oxidation of a range of arylalkanes
under mild conditions, which exhibits enzyme-like features by
imitating the structural features, active centers and catalytic
mechanism of enzymes.
[a]
Min Zhao and Prof. Dr. Chuan-De Wu
State Key Laboratory of Silicon Materials
Center for Chemistry of High-Performance & Novel Materials
Department of Chemistry
Zhejiang University
Hangzhou, 310027, P. R. China
E-mail: cdwu@zju.edu.cn
Supporting information for this article is given via a link at the end of
the document.
This article is protected by copyright. All rights reserved.

10.1002/cctc.201601606
ChemCatChem
COMMUNICATION
transferred through the 3D open channels, and the appropriate
hydrophilic and hydrophobic natures of these different pore
cages might facilitate the recognition of substrate and product
molecules for highly efficient catalysis. According to the topology
analysis method suggested by O’Keeffe and Yaghi,10 the
network structure of CZJ-6 has the pto topology which is same
with MOF-143, Cu-TCA and UNLPF-2 in the literature,11 when
CuII-L is considered as a four-coordinated node, the terphenyl
unit as three-coordinated branch point, and the paddle-wheel
{Cu2} as the four points of extension (Figure 2).
Figure 2. The three kinds of connecting joints (left) and their connections to
form the pto topology net (right) in the crystal structure of CZJ-6.
Figure 1. (A) Perspective view of the crystal structure of CZJ-6 along the a
axis. (B) A portion structure of CZJ-6, showing the substrate-accessible
porphyrin CuII sites and pore cages (the balls with different colors indicate
different cages). Color scheme: Cu, cyan balls (porphyrin Cu) and green
square pyramids (paddle-wheel Cu); O, red; N, blue; C, deep gray; H, light
gray.
PLATON calculations indicate that CZJ-6 consists of 78.8%
void space to accommodate the guest molecules.12 The
permanent porosity of CZJ-6 has been examined by N2
adsorption experiments at 77 K (Figure S4). After the acetone-
o
exchanged CZJ-6 was heated at 50 C under vacuum for 6 h,
powder X-ray diffraction (PXRD) analysis of the activated
sample showed that the diffraction pattern is basically identical
to that of the as-synthesized one (Figure S6). The activated solid
sample of CZJ-6 takes up 530 cm3 g-1 N2 at 77 K and 1 bar,
which results in a BET surface area of 394 m2 g-1.
Brownish crystals of the metalloporpyrinic MOF CZJ-6 were
synthesized by heating a mixture of H10L and copper(II) acetate
in a mixed solvent of DMF and nitric acid at 80 °C for one week.
The composition of the as-synthesized CZJ-6 was calculated on
the basis of elemental analysis, thermogravimetric analysis
(Figure S2), 1H NMR spectroscopy (Figure S3) and single crystal
structure. Single crystal X-ray diffraction analysis revealed that
CZJ-6 crystallizes in the tetragonal P42/mmc space group (Table
S1). The framework structure is built from paddle-wheel
[Cu2(COO)4(H2O)2] (abbreviated as {Cu2}) SBUs and octatopic
CuII-L metalloporphyrin ligands. In the crystal structure, the
deprotonated Cu-L ligand connects with eight paddle-wheel {Cu2}
SBUs, and the {Cu2} SBU connects with four L ligands to form a
3D non-interpenetrated network (Figure 1a). The connections
between these SBUs result in two kinds of inter-connected
nano-cages with different hydrophilic and hydrophobic natures.
As shown in Figure 1b, the first cage is built from two
neighboring porphyrin macrocycles and four paddle-wheel {Cu2}
SBUs with the pore dimension of about 1.4 nm (the distance
between two porphyrin coppers; purple balls), and the second
cage is constructed from six paddle-wheel {Cu2} SBUs with pore
dimension of about 2.3 nm (orange ball). Apparently, the
porphyrin CuII sites are readily accessible to the substrates
Oxidation of the petroleum-based hydrocarbons to form
oxygenated compounds is very important in industry.13 Among
the various established strategies, aerobic oxidation represents
the most elegant and environmentally friendly pathway for a
large scale production of invaluable oxidation products.14 The
challenge is to directly oxidize the unactivated hydrocarbons
with dioxygen under mild conditions, given the fact that the C-H
bonds are very stable. Attracted by the aerobic oxidation which
can be easily realized with enzymes under mild conditions, we
have used the aerobic oxidation of ethylbenzene as a model
reaction to study the biomimetic properties of CZJ-6. The
ethylbenzene oxidation by CZJ-6 was performed in acetonitrile
solvent at 50 C for 24 h under 1 atm O2 atmosphere. GC-MS
analysis indicates that CZJ-6 is inactive on the aerobic oxidation
reaction (Table 1, entry 1). Compared with the biocatalysis
system, the inability of CZJ-6 on the activation of molecular
oxygen should be ascribed to the lack of assistant catalysts as
electron donors. It has been demonstrated that N-
hydroxyphthalimide (NHPI) is easily abstracted the N-hydrogen
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10.1002/cctc.201601606
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COMMUNICATION
to form phthalimido-N-oxyl radical (PINO) in many oxidation
reactions.15 NHPI might act as an electron donor to prompt the
aerobic oxidation by mimicking the role of reductases in P450
catalysis. We therefore added NHPI as an assistant catalyst into
the reaction mixture. As shown in entry 2, the coupled catalyst
system efficiently prompts this oxidation reaction with 48%
acetophenone yield and remarkable selectivity (>99%).
Table 1. Aerobic oxidation of arylalkanes for the formation of phenylketones.[a]
Entry
1
Substrate
Catalyst
CZJ-6
Product
Yield/%[b]
0
Polyoxometalates (POMs) with unique features of tunability,
redox chemistry and charge distribution have been employed as
efficient catalysts in numerous reactions.16,17 The Weakley
sandwich type POMs [WM{M'(H2O)}2(MW9O34)2]12− (abbreviated
as {M3M'2W19}, where M, M' = Zn2+, Co2+, Mn2+, and Cu2+, etc.),
consisting of a d-electron metal ring belt WM'MM' between two
{B-α-MW9O34} units, exhibit similar catalytic properties with
metalloporphyrins.17 Therefore, trapping inorganic {M3M'2W19}
clusters inside the pore space of CZJ-6 might further improve
the catalytic efficiency. Since the channel diameter (2.3 nm) of
CZJ-6 is large enough to encapsulate the sandwich-type POM
{M3M'2W19} (about 1.0 × 1.0 × 1.6 nm3 in dimensions) inside the
pore space, [WZn{Co(H2O)}2(ZnW9O34)2]12− ({Zn3Co2W19}) was
introduced as a co-catalyst on the aerobic oxidation. As shown
in entry 3, it is remarkable that ethylbenzene was almost fully
oxidized into acetophenone product (92% yield) by the
combined catalyst system under mild conditions. The catalytic
properties of the combined catalyst system outperform those of
the simple mixtures of its constituents Cu-H8L, NHPI and
{Zn3Co2W19}, and NHPI/Co(OAc)2 (entries 4-8). To evaluate the
contribution of {Cu2} sites, we studied the catalytic property of
HKUST-1 with the same {Cu2} SBUs,18 which is almost identical
to that of single NHPI (entry 9). The above results demonstrate
that the high oxidation efficiency of the biomimetic platform is
unmatched by the simple mixtures of its constituents. The
combined catalyst platform can also efficiently oxidize various
arylalkanes under the mild conditions (entries 10-14).
To prove that the inside pore space and the porphyrin copper
sites in CZJ-6 are accessible, we have used substrate
ethylbenzene and product acetophenone as probes to study the
sorption ability of the activated CZJ-6. When a solvent free
sample was immersed in ethylbenzene and acetophenone for 6
hrs at room temperature, GC-MS analysis revealed that the
pores of CZJ-6 are accessible to ethylbenzene and
acetophenone molecules with the uptakes of 120 and 117 wt%,
respectively. We also studied the selective sorption ability of
CZJ-6 to ethylbenzene and acetophenone by adding an
activated sample into their mixture (1:1 molar ratio). GS-MS
analysis indicates that CZJ-6 preferably takes up ethylbenzene
over acetophenone with molar ratio of 2.6. Such preferred
sorption of ethylbenzene reactant over acetophenone product
can facilitate the accumulation of substrate and the release of
product in the reacting pores, and thus to improve the catalytic
efficiency. Moreover, after the reaction proceeded for 12 h, the
catalysis was intentionally interrupted, and the solid catalyst was
collected by centrifugation. GC-MS analysis showed that the
desorbed ethylbenzene and acetophenone from this reacted
solid CZJ-6 is about 1.45 molar ratio. The above results
demonstrate that the easy access of the inside pore space and
the selective accumulation of ethylbenzene substrate into the
pore space have maximized the oxidation efficiency of the
immobilized porphyrin Cu(II) sites on the pore surfaces of CZJ-6.
2
CZJ-6/NHPI
CZJ-6/NHPI/
48
92
12
39
41
26
59
13
73
95
99
76
97
89[c]
3
{Zn3Co2W19
}
NHPI
4
5
NHPI/Co(OAc)2
NHPI/
6
{Zn3Co2W19
}
7
Cu-H8L/NHPI
Cu-H8L/NHPI/
8
{Zn3Co2W19
}
HKUST-1/NHPI
9
CZJ-6/NHPI/
10
11
12
13
14
15
{Zn3Co2W19
}
CZJ-6/NHPI/
{Zn3Co2W19
}
CZJ-6/NHPI/
{Zn3Co2W19
}
CZJ-6/NHPI/
{Zn3Co2W19
}
CZJ-6/NHPI/
{Zn3Co2W19
}
CZJ-6/NHPI/
{Zn3Co2W19
}
[a] Arylalkanes (0.25 mmol), CZJ-6 (0.0005 mmol), NHPI (0.025 mmol),
{Zn3Co2W19} (0.0005 mmol) and TBAB (0.006 mmol) in acetonitrile (2 mL)
were stirred under an O2 atmosphere (balloon) at 50 oC for 24 h. [b] Yield%
was determined by GC-MS. [c] The seventh cycle.
After a mixture of CZJ-6, NHPI, {Zn3Co2W19} and TBAB in
acetonitrile was heated at 50 C under stirring for 24 h in the O2
atmosphere, ethylbenzene was added into the filtrate, which was
reacted for another 24 h. GC analysis showed that the
conversion of ethylbenzene is identical to the result catalyzed by
NHPI. This result demonstrates the heterogeneous catalytic
nature of the catalyst system. The combined solid can be easily
recovered by centrifugation, and subsequently used in the
successive runs for 7 cycles with almost retained high efficiency
(Table 1, entry 15; Figure S7). A PXRD pattern of the recovered
solid showed that the structural integrity of CZJ-6 is almost intact
(Figure S6). Additionally, UV-Vis spectroscopy of the plasma
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10.1002/cctc.201601606
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COMMUNICATION
demonstrates that the POM moieties did not leach off from CZJ-
6 during the reaction, which has been confirmed by EDX spectra
(Figures S8 and S9). The remarkable catalytic efficiency and
sustainability of the combined catalyst platform further
encouraged us to study the kinetic behavior by using large scale
of NHPI, whereas NHPI is able to donate the N-hydrogen to
prompt metalloporphyrin catalysis. The sandwich-type POMs
have been regarded as inorganic equivalents and complements
of metalloporphyrins since they exhibit similar catalytic
properties in many oxidation reactions.17 Therefore, the aerobic
of substrate. As shown in Figure S10, the turnover number (TON) oxidation efficiency is significantly improved in the presence of
reaches to 25600 after 120 hrs without loss of the catalytic
activity in the following runs.
POM {Zn3Co2W19}. The catalytic properties of the biomimetic
platform are much superior to other reported heterogeneous
catalysts with transition metal catalytic sites, such as MOFs,
metal oxides, immobilized metal complexes and others, for the
aerobic oxidation of arylalkanes, in terms of oxidation efficiency
and selectivity, and catalytic conditions.19 Compared with
enzymatic catalysis, the biomimetic catalyst platform is more
economic because the oxygen atoms of O2 are both participated
in the oxidation reaction (PhCH2CH3 + O2 → PhCOCH3 + H2O),
whereas one oxygen atom of O2, reduced by the reductase, is
sacrificed in the enzymatic catalysis (PhCH2CH3 + 2O2 + 4H+ +
4e → PhCOCH3 + 3H2O).
In summary, to make use of the eight-branched
metalloporphyrin Cu-L ligand to connect with paddle-wheel {Cu2}
SBUs, we successfully constructed a porous metalloporphyrinic
framework material, consisting of two kinds of hydrophilic and
hydrophobic nano-cages. To realize highly efficient biomimetic
activation of molecular oxygen, NHPI and POM were introduced
as the co-catalysts to form a combined catalyst system. The
biomimetic platform exhibits enzyme-like features in the aerobic
oxidation of arylalkanes under mild conditions with very high
efficiency, selectivity and sustainability. This work indicates that
the use of combined catalyst system, consisting of multiple
active sites, represents one of the most feasible pathways to
mimic enzymatic catalysis, and thus to realize highly efficient
catalysis under mild conditions.
Scheme 1. Proposed catalytic cycles for the aerobic oxidation of ethylbenzene
by the biomimetic metalloporphyrin and NHPI catalyst platform.
As shown in Scheme 1, it has been generally accepted the
aerobic oxidation cycle of P450.9 At first, the porphyrin metal
binds with a labile dioxygen by complexation, and then is
reduced by its redox partner,
a reductase, followed by
protonation to give a hydroperoxo intermediate. The second
electron is transferred from the reductase to lead to heterolytic
cleavage of the O–O bond in the presence of a proton, which
forms the highly active oxo-metal intermediate. The oxygenated
metalloporphyrin inserts an oxygen into the methylene C-H bond
of ethylbenzene to realize aerobic oxidation. It is very clear that
the biocatalyst, involving in a complex multiple active site system,
requires two protons and two electrons per catalytic cycle to
achieve highly efficient aerobic oxidation. Because the
metalloporphyrinic MOF does not consist of such assistant
catalytic site and the O-O bond cleavage requires high
temperature, it is not surprise that CZJ-6 cannot directly activate
molecular oxygen under mild conditions. As suggested in the
literature, NHPI is easily abstracted the N-hydrogen to form
PINO in the oxidation catalysis.15 The hydrogen might act as a
combined proton and electron donor to prompt metalloporphyrin
oxidation catalysis. In other word, NHPI has the properties to
mimic the reductases in the biological system. Therefore, NHPI
represents an ideal assistant catalyst, acting as a proton- and
electron-transfer mediator, for the aerobic oxidation with
metalloporphyrins. Moreover, the resulted PINO is able to initiate
the radical propagation of aerobic oxidation, and returns to NHPI
by abstraction of a hydrogen from hydrocarbon, similar to that of
the literature oxidation process. It is very interesting that
metalloporphyrin species can prompt the hydrogen abstraction
Acknowledgements
This work was financially supported by the National Natural
Science Foundation of China (grant nos. 21373180 and
21525312).
Keywords: Biomimetic Catalysis • Metalloporphyrin • Metal-
Organic Framework • Polyoxometalate • Synergistic Catalysis
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10.1002/cctc.201601606
ChemCatChem
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
A
combined biomimetic platform,
Min Zhao, Chuan-De Wu*
consisting of metalloporphyrinic
Page No. – Page No.
framework, N-hydroxyphthalimide and
polyoxometalate, exhibits enzyme-like
features in the aerobic oxidation of
arylalkanes under mild conditions with
very high efficiency, selectivity and
Biomimetic Activation of Molecular
Oxygen with a Combined
Metalloporphyrinic Framework and
Co-catalyst Platform
sustainability
by
imitating
the
structural features, active sites and
catalytic mechanism of enzymes, in
which up to 99% yield and 25600
turnovers have been realized.
This article is protected by copyright. All rights reserved.