Mn(III)-Porphyrin Containing Heterogeneous Catalyst based on Microporous Polymeric Constituents as a New Class of Catalyst Support

Article abstract of DOI:10.1002/cctc.201800973

Mn(III)-porphyrin containing #heterogeneous catalyst based on microporous polymeric constituents as a new class of #catalyst support from Korea University and Seoul National University of Science and Technology.

Full text of DOI:10.1002/cctc.201800973

Accepted Article
Title: Mn(III)-Porphyrin Containing Heterogeneous Catalyst based on
Microporous Polymeric Constituents as a New Class of Catalyst
Support
Authors: Jigyoung Yi, Ha Young Jeong, Dae Yong Shin, Cheal Kim,
and Suk Joong Lee
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10.1002/cctc.201800973
ChemCatChem
COMMUNICATION
Mn(III)-Porphyrin Containing Heterogeneous Catalyst based on
Microporous Polymeric Constituents as a New Class of Catalyst
Support
Jigyoung Yi,[a] Ha Young Jeong,[b] Dae Yong Shin,[a] Cheal Kim*[b] and Suk Joong Lee*[a]
Dedication ((optional))
Abstract: A new class of heterogeneous catalyst, Mn(III)-PIM (1),
using polymer with intrinsic microporosity (PIM) as a support was
developed. It shows efficient catalytic activity for olefin epoxidation
with good reusability. Remarkably, recycling enabled one batch of 1
to be continuously used for all substrates. It was proposed that
Mn(V)=O and Mn(IV)=O are key active oxidants.
which results in a significant number of pores and large surface
area.13 The synthesis of a new class of PIMs with highly
accessible inherent surface areas and pores has recently
received significant attention. These PIMs have the potential for
several practical applications upon the incorporation of moieties
with a wide range of chemical functionalities.14 In particular, the
incorporation of a molecular catalyst that exploits their intrinsic
porosity may generate a highly tunable platform for a variety of
single-site catalytic reactions.15 Well-controlled catalytic
platforms are critical for the development of practical
heterogeneous catalysts. Accordingly, the synthesis of materials
with well-defined pores has recently been considered to be one
of the most promising techniques to maximize the full catalytic
potential.16
Herein, we report the preparation of a new class of catalytic
PIM containing an immobilized Mn(III)-porphyrin as a new
recyclable heterogeneous catalyst for the oxidation of various
olefins.17 Although porphyrinic complexes of Mn(III) are well-
known catalysts for the effective oxidation of a variety of olefins,
they often degrade during the reaction through ligand oxidation
or µ-oxo dimer formation.18 We envisage that immobilization of
the catalyst in a PIM framework may prevent this disadvantage,
resulting in an efficient catalyst system.
Owing to their large internal surface area, porous materials often
provide a tremendous catalytic advantage over their non-porous
analogs. Recently, tremendous research effort has been
focused on developing a variety of porous materials, such as
metal-organic frameworks (MOFs).1 Intensive studies have been
conducted on a wide range of applications of porous materials
including catalysis,2 gas storage,3 chemical sensing,4 and
chemical separations.5 However, they are often reported to
suffer from relatively low chemical stability,6 which limits their
practical potential.7 Recently, a new class of porous materials
called porous organic polymers (POPs)8 has received
considerable attention because of their high chemical stability;
this arises because their preparation involves the generation of
strong and irreversible covalent bonds such as C–C, C–N,
and/or C–O bonds9 that are the foundation of the hyper-
crosslinked polymeric materials. POPs are constructed through
the incorporation of multi-topic monomers into step-growth and
chain-growth polymerization reactions to generate cross-links
that yield three-dimensional (3D)–network materials.10
Recently, a new type of porous polymeric material has
received considerable attention because of its fascinating
structural features including high porosity and surface area.11
Polymers are not generally porous because they have high
intermolecular attraction and sufficient structural flexibility to
eliminate any void space.12 However, a new class of porous
polymeric materials has emerged: Polymers with intrinsic
microporosity (PIMs) are extremely rigid and distorted
macromolecules with high porosity and surface area because of
ineffective packing. Their rotational flexibility is restricted along
the polymer backbone because the building blocks contain
constrained sites, such as a binaphthalene or spirocenter unit,
Scheme 1. Preparation of Por-PIM and Mn(III)-PIM (1).
Main Text Paragraph. A new porphyrin-embedded PIM,
Por-PIM, was prepared by following a modified literature
procedure19 that involves the formation of rigid dibenzodioxane
units via aromatic nucleophilic substitution.
A solution of
5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (L1) and 1,1'-
binaphthalene-2,2',3,3'-tetraol (L2) in anhydrous N-methyl-2-
pyrrolidinone (NMP) with K2CO3 as a base was heated at 80 °C
for 24 h under a nitrogen atmosphere (Scheme 1). After
washing intensively with water, acetone, DMF and MeOH, Por-
PIM was obtained as a dark brown solid (86% yield; see the
Supporting Information section for detailed syntheses and
characterizations). The nitrogen adsorption isotherm of Por-PIM
at 77 K revealed a relatively high surface area of 1028 m2g−1
with a mean pore diameter of 5.14 nm (Fig. 1). Subsequent
[a]
[b]
Ms. J. Yi, Mr. D.Y. Shin, and Prof. S. J. Lee
Department of Chemistry
Korea University
Seoul 136-701, Republic of Korea
E-mail: slee1@korea.ac.kr
Mr. H. Y. Jeong, Prof. C. Kim
Dept. of Fine Chemistry
Seoul National University of Science and Technology
Seoul 136-743, Republic of Korea
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
.
metalation with MnCl2 4H2O in NMP afforded Mn(III)-PIM (1) in a
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10.1002/cctc.201800973
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high yield (98%) with a surface area of 823 m2g−1 and mean
pore diameter of 2.49 nm (Fig. 1). The small decrease observed
in the surface area and pore diameter upon metalation was
attributed to the addition of mass (Table S1).
catalyst during the epoxidation of styrene was also studied
(Table S3): The catalyst was successfully used for several
cycles, suggesting that it is very stable and robust. We also
performed an additional control reaction to assess the potential
catalytic contribution of Mn(III) species that leach from 1: First,
we filtered the reaction solution after the epoxidation reaction of
styrene and then analyzed the filtrate using ICP. The results
showed no evidence of any Mn(III) species, which suggests that
the catalytic reactive species is 1 and not leached Mn(III).
Infrared (IR) and solid-state nuclear magnetic resonance
(NMR) spectroscopic analyses of Por-PIM clearly show
evidence of the formation of a polymer.20 In the IR spectra of
Por-PIM and 1 (Fig. S1), the stretches of the hydroxyl groups at
~3490 cm−1 are much less intense than those of the parent 1,1'-
binaphthalene-2,2',3,3'-tetraol (L2) material, suggesting the
formation of dibenzodioxane units. In the 13C cross-polarization–
magic angle spinning (CP-MAS) NMR spectrum of Por-PIM, the
peaks that occur around 30 and 225 ppm (from the spinning side
bands) and several overlapping peaks between 120 and 150
ppm (from the aromatic carbon atoms) clearly support the
formation of dibenzodioxane units containing binaphthalene and
porphyrin groups (Fig. S2).21 Additionally, the solid-state 19F
MAS NMR spectrum of Por-PIM shows distinctive isotopic peaks
at −128, −148, and −175 ppm, which also supports the formation
of dibenzodioxane units (Fig. S3).22
Next, we performed catalytic epoxidation of a wide variety
o
of olefins by SPhIO using 1 in CH2Cl2 at 20 C. By recovering
the catalyst, we successfully used one batch of 1 for all the
substrates and the results of epoxidation reactions are displayed
in Table 1. Further reusability study of the catalyst was verified
in Table S3. Cyclic olefins, including cyclopentene,
cycloheptene, and cyclooctene, were converted to their
corresponding epoxides with moderate to high yields (48.4% to
90.9%, entries 1–3). In contrast, cyclohexene gave cyclohexene
oxide (68.1%) as the major product with small amounts of 2-
cyclohexen-1-ol (4.5%) and 2-cyclohexen-1-one (3.0%) as by-
products (entry 4). This result indicates that free-radical-type
oxidation was only a minor contributor to the epoxidation
reaction.24 Terminal alkenes, 1-hexene and 1-octene, which are
usually the least reactive olefins towards metal-catalyzed
epoxidation,25 were moderately oxidized to their corresponding
epoxides (38.7 and 38.5%, entries 5 and 6). cis-2-Octene and
cis-2-hexene were used as substrates to examine the
stereochemistry of the epoxidation reaction; the results showed
that cis-2-octene oxide and cis-2-hexene oxide were exclusively
produced in yields of 66.4% and 69.8% (entries 7 and 9),
respectively. Reactions using trans-2-octene and trans-2-hexene
resulted in the production of only trans-2-octene oxide and trans-
2-hexene oxide, respectively (21.1% and 80.4%, entries 8 and
10).
Styrene was primarily oxidized to styrene epoxide (51.8%,
entry 11) along with small amounts of phenylacetaldehyde
(14.3%). While cis-stilbene was converted to a mixture of cis-
stilbene oxide (25.0%, entry 12), 2-phenylacetophenone (4.4%),
and trans-stilbene oxide (4.6%), trans-stilbene was oxidized to
trans-stilbene oxide (30.2%, entry 13) as a major product with
minor amounts of 2-phenylacetophenone (5.1%). The product
distributions of olefins with aromatic moieties suggest that either
the peroxyl radical or Mn(IV)=O species was partially involved as
the epoxidizing reactive oxidants. This is because these species
are expected to produce non-stereospecific or radical-type
rearranged products during the epoxidation reactions of
aromatic olefins.26 These results led us to assume that two
different reactive species, Mn(V)=O (3) and Mn(IV)=O (4), might
be generated in these catalytic systems with 4 resulting in non-
stereoretentive epoxidation (Scheme S1).
PIM
Por-PIM
Mn(III)-PIM
Mn(III)-PIM
800
600
400
200
0
0.0
0.2
0.4
0.6
0.8
1.0
P/Po
Figure 1. N2 adsorption (filled markers) and desorption (empty markers)
isotherms of Por-PIM (red) and 1 (blue).
Inductively coupled plasma atomic emission spectroscopy
(ICP-AES) analysis of digested 1 indicates a Mn content of 6.43
wt.%, while energy dispersive X-ray spectroscopy (EDX)
analysis showed a Mn content of 5.82 wt.% (Fig. S4), as
summarized in Table S1. As a control, Por-PIM was also
analyzed via ICP-AES; no Mn was evident. To assess the
thermal stability of the polymers, thermal gravimetric analysis
(TGA) was conducted. As shown in Figure S5, both Por-PIM
and 1 are thermally stable up to 400 °C with a small continuous
weight loss at low temperatures due to the removal of free
solvent molecules. Degradation of the irregular and/or relatively
short polymeric structures slightly broadens the thermal
decomposition range within which the polymer networks
collapse.23
To elucidate the nature of the reactive intermediates
responsible for this epoxidation reaction, we investigated the
substituent electronic effects on the epoxidation rate using
styrene and four para-substituted styrenes. Assay of a Hammett
plot gave a  value of −0.42 (Fig. 2), which suggests that the
active oxidants have an electrophilic character. This  value is
greater than those reported for the epoxidation of styrene with
Mn(III) salen ( = −0.3)26 and Mn(III) tetraphenylporphyrin ( =
−0.41),27 and somewhat lower than those of Re4 cluster–
To examine the catalytic ability of 1, it was tested for the
epoxidation
of
styrene
using
1-(tert-butylsulfonyl)-2-
iodosylbenzene (SPhIO) as an oxidant with various solvent
systems (Table S2). The highest yield of styrene oxide (51.8%)
o
was observed in CH2Cl2 with a reaction time of 2 h at 20 C. We
also verified that direct oxidation of the substrate by the oxidant
was insignificant without a catalyst. The recyclability of the
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10.1002/cctc.201800973
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supported Mn(H,MePyTACN)(CF3SO3)2 ( = −0.67; H,MePyTACN=
Table S4. The ratios of cis- to trans-2-octene oxides increased
with increasing substrate concentration from 10 to 80 mM (1.4 to
2.2, entries 1–4), which indicates that the Mn(III)-OIR species (2)
might be involved in the epoxidations. This is evident from the
preference of 2 for cis-olefins over trans-olefins because of the
steric hindrance between the trans substrate and 2.30
1-methyl-4-methyl(2-pyridyl)-1,4,7-triazacyclononane)28
and
Mn(III) saloph ( = −0.66; saloph = N,N’-o-phenylenebis(Sali-
cylidenaminato)).29
Based on our reactivity studies, the most possible
mechanism for the formation of the reactive intermediates
responsible for olefin epoxidation is that shown in Scheme S1:
First, SPhIO reacts with 1 to produce 2, which then undergoes
either heterolysis or homolysis to afford Mn(V)=O (3) or
Mn(IV)=O (4) intermediates. The Mn(V)=O species generated
from heterolysis (pathway (a) of Scheme S1) might be
responsible for the high epoxide yields and stereochemical
retention. In contrast, the Mn(IV)=O species generated from
homolysis (pathway (b) of Scheme S1) might promote radical-
type oxidation through the formation of allylic oxidation products,
which generates a loss of stereospecificity. With increasing
Figure 2. Hammett plot for selective epoxidation of styrene to para-substituted
styrenes by Mn(III)-PIM (1) with SPhIO.
concentration of olefin,
2 might be a possible reactive
intermediate for epoxidation (pathway (c)). Therefore, 3 and 4
might act simultaneously as key active oxidants, while the
Mn(III)-OIR species contributes to the epoxidation reaction at
high olefin concentrations.31
For a control, molecular catalyst Mn(III)-porphyrin (Mn(III)-
L1) was prepared and its catalytic performance in cyclohexene
Competition experiments were performed to obtain more
information about the selectivity of cis- and trans-2-octene
toward the active intermediates. The results are displayed in
Table 1. Olefin epoxidation by Mn(III)-PIM (1
) with SPhIO in CH2Cl2 at 20 oC.[a],[b]
Mn(III) catalyst 1[c]
Conversion (%) Yield (%)
48.4 ± 3.0
Entry
Substrate
Product
1
2
3
4
cyclopentene
cycloheptene
cyclooctene
cyclohexene
epoxide
79.2 ± 4.3
96.5 ± 4.0
59.1 ± 7.7
68.0 ± 3.7
epoxide
90.9 ± 0.7
55.5 ± 2.6
68.1 ± 2.4
3.0 ± 0.1
4.5 ± 0.1
38.7 ± 0.3
38.5 ± 0
69.8 ± 5.9
trace
epoxide
epoxide
2-cyclohexene-1-one
2-cyclohexene-1-ol
epoxide
5
6
7
1-hexene
38.7 ± 0.7
39.5 ± 4.0
66.2 ± 6.4
1-octene
epoxide
cis-2-hexene
cis-oxide
trans-oxide
8
9
trans-2-hexene
cis-2-octene
trans-oxide
79.8 ± 5.0
66.4 ± 2.0
80.4 ± 5.5
66.4 ± 0.3
trace
cis-oxide
trans-oxide
10
11
trans-2-octene
styrene
trans-oxide
32.6 ± 0
21.1 ± 0.7
51.8 ± 3.0
trace
epoxide
68.9 ± 5.7
benzaldehyde
phenylacetaldehyde
cis-stilbene oxide
trans-stilbene oxide
benzaldehyde
2-phenylacetophenone
trans-stilbene oxide
benzaldehyde
2-phenylacetophenone
14.3 ± 0
25.0 ± 4.1
4.6 ± 0.4
trace
12
13
cis-stilbene
75.7 ± 2.9
66.9 ± 1.5
4.4 ± 0.2
30.2 ± 1.8
trace
trans-stilbene
5.1 ± 0.2
[a]Reaction conditions: olefin (2.2 × 10–2 mmol), catalyst (2.2× 10–3 mmol), SPhIO (2.2× 10–2
mmol), and a reaction time of 2 h. [b]One batch of
[b]Based on substrate
1 was used for all substrates by recycling.
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oxidation was compared with 1. As shown in Figure S7, the
initial catalytic activity of Mn(III)-L1 was greater than that of 1,
but it was slowly reduced and no further reaction took place after
10 min of reaction time. Presumably, the degradation of Mn(III)-
L1 by the formation of less active dimer and/or aggregated
species and oxidation of ligand is responsible for this
observation.32 The site isolation strategy is effective to reduce
the potential of catalyst deactivation and thus increase catalytic
activity and stability.
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In summary, we designed and synthesized a new class of
PIM as a platform for molecular catalyst. Mn(III)-PIM (1) showed
efficient catalytic activity towards olefin epoxidation and good
reusability using SPhIO as an oxidant. Remarkably, recycling
enabled one batch of 1 to be continuously used for all substrates.
Mechanistic studies, including product analysis, Hammett plot,
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might act simultaneously as key reactive oxidants while the
Mn(III)-OIR intermediate contributes partially to the epoxidation
reaction under the high olefin concentrations.
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mmol), Mn(III)-PIM (1) (2.2x10-3 mmol), and solvent (CH2Cl2, 1 mL). The
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and Key Research Institute Program (NRF2010-0020209)
through the National Research Foundation of Korea (NRF) and
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Keywords: PIM • microporous • heterogeneous • epoxidation •
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Entry for the Table of Contents (Please choose one layout)
Layout 1:
COMMUNICATION
A new class of heterogeneous
catalyst, Mn(III)-PIM (1), using
polymer with intrinsic microporosity
(PIM) as a support was developed. It
shows efficient catalytic activity for
olefin epoxidation with good
reusability. Remarkably, recycling
enabled one batch of 1 to be
continuously used for all substrates
without losing activity.
Jigyoung Yi, Ha Young Jeong, Dae
Yong Shin, Cheal Kim* and Suk Joong
Lee*
Page No. – Page No.
Mn(III)-Porphyrin Containing
Heterogeneous Catalyst based on
Microporous Polymeric Constituents
as a New Class of Catalyst Support
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