Porous aromatic frameworks (PAFs) as efficient supports for N-heterocyclic carbene catalysts

Article abstract of DOI:10.1039/c6cy00597g

Porous polymeric aromatic frameworks (PAFs) have high porosity and surface area, as well as high physicochemical stability; such characteristics are important in the design of heterogeneous catalysts with high catalytic efficiency and recyclability. This paper presents the synthesis, characterization, post-functionalization and catalytic performance of the resulting modified PAFs based on tetraphenyladamantane (PAF_Ad), tetraphenylmethane (PAF_C) and 9,9′-spirobisfluorene (PAF_spf) nodes. The PAFs were obtained by the Suzuki-Miyaura cross-coupling under microwave heating, and were sequentially reacted with 1-(chloromethoxy)octane and 1-mesityl-1H-imidazole or 2-(1H-imidazol-1-yl)pyridine to yield the corresponding imidazolium chloride derivative (PAF-Im) which readily formed stable N-heterocyclic carbene (NHC) iridium and ruthenium complexes (PAF-(NHC)Ir, PAF-(NHC)Ru). The materials were characterized by solid-state NMR spectroscopy, FTIR spectroscopy, and textural analysis. The PAF-(NHC)M materials display excellent catalytic performance in the N-alkylation of amines with alcohols and transfer hydrogenation of ketones over multiple catalytic cycles.

Full text of DOI:10.1039/c6cy00597g

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E. VERDE SESTO, A. M. Rasero-Almansa, M. Iglesias and F. Sánchez, Catal. Sci. Technol., 2016, DOI:
10.1039/C6CY00597G.
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Porous Aromatic Frameworks (PAFs) as efficient supports for N‐
heterocyclic carbene catalysts
Received 00th January 20xx,
Accepted 00th January 20xx
Elizabeth Rangel‐Rangel,a Ester Verde‐Sesto,a,† Antonia M. Rasero‐Almansa,a,b Marta Iglesias,a,*
Félix Sánchez.b,*
DOI: 10.1039/x0xx00000x
Porous polymeric aromatic frameworks (PAFs) have high porosity, surface area, and high physicochemical stability; such
characteristics are important in the design of heterogeneous catalysts with high catalytic efficiency and recyclability. This
paper presents the synthesis, characterization, post functionalization and catalytic performance of resulting modified PAFs
based on tetraphenyladamantane (PAFAd), tetraphenylmethane (PAFC) and 9,9'‐spirobisfluorene (PAFspf) nodes. PAFs were
obtained by the Suzuki–Miyaura cross‐coupling under microwave heating, and were sequentially reacted with 1‐
(chloromethoxy)octane and 1‐mesityl‐1H‐imidazole or 2‐(1H‐imidazol‐1‐yl)pyridine to yield the corresponding imidazolium
chloride derivative (PAF‐Im) which readily formed stable N‐heterocyclic carbene (NHC) iridium and ruthenium complexes
(PAF‐(NHC)Ir, PAF‐(NHC)Ru). The materials were characterized by solid‐state NMR spectroscopy, FTIR spectroscopy, and
textural analysis. The PAF‐(NHC)M materials display an excellent catalytic performance in the N‐alkylation of amines with
alcohols and transfer hydrogenation of ketones over multiple catalytic cycles.
www.rsc.org/
factors to use PAFs as multi‐functional catalysts to carry out
catalytic reactions. In these aromatic nodes is possible to
incorporate different functions, isolated, and stabilized,
Introduction
The development of new stable, robust, and highly accessible
porous materials with associated functionalities in their
framework remains a key topic in material science especially
for applications in adsorption, separation, catalysis, energy
storage, sensors, electronic or photoluminescence devices1
The preparation of this type of porous materials implies the
use of suitable building units to create networks through
appropriate synthetic procedure.2 Thus, materials as metal‐
organic frameworks (MOFs)3 or porous organic polymer
(POPs),4 with or without metals in their main structure have
been reported. Within the POPs materials it is possible to find
hyper‐crosslinked polymers (HCPs),5 polymers with intrinsic
microporosity (PIMs),6 or covalent organic frameworks
(COFs).7 In this group of materials, those based on totally
aromatic units, named porous aromatic frameworks (PAFs),
are particularly important and are more robust and stable than
conventional COFs or even MOFs. The porosity,
physicochemical stability and the possibility to use the rigid
planar aromatic rings as reliable platform linkers are key
without blocking internal pore volume.8
Homogeneous catalysts play an important role in the field of
modern catalysis. However, most precious organometallic
catalysts have not been widely used due to their complicated
synthesis, recycling problem, and thus the metal
contamination of the products.9 So far, the main method of
recycling organometallic complexes is the heterogenization of
the homogeneous catalysts. For instance, in the classical
supporting method, the catalyst is anchored to various kinds of
supports, such as silica‐based materials10 and magnetic
nanoparticles.11 POPs,12 PAFs,13,88 and MOFs,14‐16 have emerged
as versatile materials which can be used as supports of
catalysts because of its porous nature and high surface area
and easily modified by post‐functionalization and catalysts
were loaded via covalent8 or noncovalent interactions.17,18
The successful isolation and characterization of
a N‐
heterocyclic carbene (NHC) in 199119 opened up a new class of
organic compounds for research today, NHCs today rank
among the most powerful tools in organic chemistry, with
numerous applications in commercially important processes.20
Transition metal complexes of NHCs have attracted great
interest offering a good opportunity to tune the reactivity and
selectivity of transition metal catalysts.21 Their catalytic
applications in various organic transformations, including C‐C
bond and C‐N bond formations,22 olefin metathesis,23
a. Instituto de Ciencia de Materiales de Madrid, ICMM‐CSIC, Sor Juana Inés de la
Cruz, 3, Cantoblanco, 28049 Madrid, Spain.
b. Instituto de Química Orgánica, IQOG‐CSIC. Juan de la Cierva, 3, 28006 Madrid,
Spain.
† Present address: Adolphe Merkle Institute, Chemin des Verdiers 4, CH‐1700
Fribourg, Switzerland
Electronic Supplementary Information (ESI) available: Experimental details on the oligomerization and polymerization of alkenes,24 have been
preparation and characterization of the PAF materials, additional tables and
figures are included. See DOI: 10.1039/x0xx00000x
studied widely. Nevertheless, most of them are synthesized
through multiple steps and can be used only one time in
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homogeneous catalysis. Since NHCs and transition metals are synthesized by a palladium catalyzed Suzuki‐MViyieawuArraticlecrOonslinse‐
expensive reagents, heterogenized NHC metal complexes are coupling reaction between tetrakis(4D‐iOoId: o10p.1h0e3n9y/Cl)6mCeY0th05a9n7eG,
attractive due to their reusability and the fact that the catalyst 1,3,5,7‐tetrakis(4‐iodophenyl)adamantane
or
2,2',7,7'‐
is regenerated.25 The strong

‐electron‐donating properties of tetraiodo‐9,9'‐spirobisfluorene and 1,4‐phenylenediboronic
NHCs allow the formation of very strong NHC–metal bonds acid under MW heating at 145 oC (the reactions were
and preventing the decomposition of the catalyst.26,27 The high quantitative in all the cases, at least ten batches for the
dissociation energies of the metal–carbon bonds in NHC–metal preparation of each material were carried out in scale of 200
complexes make NHCs good ligands for heterogeneous mg, experimental details are included in supplementary
systems.28 Various supports have been extensively used to information).8
heterogenize NHCs, which includes polymers, self‐supported PAFs‐CH2Cl (scheme 1) were obtained by reaction of the
poly NHCs, silica and NPs.29,30 With our continuing studies to corresponding
parent
PAF
materials
with
1‐
heterogenize homogeneous catalysts on porous matrices, in (chloromethoxy)octane in presence of TiCl4 yielding the
particular NHC‐catalysts,31,32 herein we have chosen different chloromethylated derivative (PAF‐CH2Cl). FTIR spectra of PAFs
‐
PAFs to be used as new supports for N‐heterocyclic carbene CH2Cl display two characteristic absorption bands at 1264 cm‐1
ligands. We describe a procedure for the generation of and 670 cm‐1 corresponding to the C‐Cl bond (Figure S1‐S2).33
imidazolium‐containing porous materials (PAF‐Im) and the 13C‐NMR shows the characteristic signals for the carbon atom
corresponding Metal‐NHC compounds (PAF‐(NHC)M) (Figure connected with the phenyl group (Ar‐C) of PAFC and PAFspf at
1) and their characterization at a molecular level. Finally we
∼67 ppm and peaks between 125 and 160 ppm (aromatic
used the materials as catalysts in standard transfer hydrogen carbons) (Figure S3a‐i).
reactions. They displayed activities similar to their In a second stage (scheme 1), a mixture of PAF‐CH2Cl (0.7
homogeneous homologues combined with the widely mmol Cl/g) and 1‐mesityl‐1H‐imidazole or 2‐(1H‐imidazol‐1‐
recognized advantages of heterogeneous catalysts (recycling yl)pyridine (3 mmol) in toluene (30 mL) were stirred at reflux
and separation of products). Heterogenized PAFs‐NHC‐ for 2 days. After being cooled to room temperature, the
complexes have great potential, and development of reaction mixture was filtered, and the solid washed thoroughly
recyclable catalysts is highly desirable for sustainable and dried to afford the imidazolium chloride‐supported PAF
chemistry.
(PAF‐Im) with an imidazolium loading of 1.0‐3.2 mmol/g
depending from imidazole, as determined by the nitrogen
content from elemental analysis (the analytical data of the
supported imidazolium salts are listed in Table S1, it is very
well known that in conjugated porous polymers lead to bad
combustion and incorrect values of carbon and carbon‐
hydrogen ratio34)..
PAFs‐Im result porous amorphous materials and were fully
characterized by N2 adsorption/desorption, 13C solid‐state
NMR spectroscopy, FTIR, and X‐ray diffraction (see supporting
Information). All data were consistent with the quantitative
formation of imidazolium functionalities with no degradation
of the material. FTIR showed two new absorption bands at
1546 cm‐1 and 1155 cm‐1 which characterize the ring vibration
and the bond bending vibration of the imidazolium groups (2‐
C‐H), respectively and provided clear evidence for the
attachment of the ligands (Figures S1‐S2).33,35 13C‐NMR showed
a peak at
the ‐CH3 group, a signal at
atom connected with the phenyl group (Ar‐C), (67 ppm for
PAFspf and the peak at 39 ppm due to the aliphatic carbons
∼
22 ppm which corresponds to the carbon atom of
∼
65 ppm assigned to the carbon
Figure 1. Schematic representation of the PAF‐(NHC)M from this work.
)
∼
of adamantine nucleus. Signals between 120 and 160 ppm
were the aromatic groups. The characteristic imidazolium
(NCN) carbon,36 which was overlapped with other peaks,
Results and discussion
appeared at 152 ppm (157 ppm for PAFAd, 158 ppm for PAFspf
(Figures S3a‐i).
)
PAFs‐Post‐functionalization
Synthesis of NHC‐precursors
PAFs‐supported NHC‐metal complexes were prepared in
several steps as shown in schemes 1‐2. Thus, PAFs were
2 | J. Name., 2012, 00, 1‐3
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DOI: 10.1039/C6CY00597G
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R
N
Cl
N
Cl
N
N
R
CH3(CH2)7OCH2Cl
TiCl4, CHCl3, r.t.
methyl-iso-butylketone, reflux
PAFAd, PAFC
PAFAd-CH2Cl, PAFFC-CH2Cl
PAF Ad-Im, PAFC-Im
: Adamantane, C
R
N
Cl
N
Cl
R:
R:
Im: IMes
Im: IPy
N
PAFspf
PAFspf-CHH2Cl
PAFspf-Im
Scheme 1. Preparation of PAF‐imidazolium chlorides: IMes, 1‐mesityl‐1H‐imidazole or IPy, 2‐(1H‐imidazol‐1‐yl)pyridine, methyll‐iso‐butylketone, reflux, 24 h.
The iridium content determined by inductively coupled
plasma‐atomic emission spectrometer analysis (ICP‐AES) was
PAF‐iridium(I) and ruthenium(II) complexes
PAF‐Imidazolium were converted into corresponding PAF
–
found 0.2 mmol/g (Table S2). Treatment of PAF‐Im with
o
(NHC)M complexes (PAF‐IMesIr, PAF‐IPyIr, PAF‐IMesRu, PAF‐ potassium hexamethyldisilazide (in toluene at ‐30 C) for 2 h,
‐
IPyRu) according to similar procedures reported in the warming to room temperature and posterior addition of a
literature,36 and the preparation is shown in Scheme 2. solution of [RuCl2(p‐cymene)]2 with stirring at 100 oC
Hereinafter, we will continue only with PAFC and PAFspf overnight, led to the formation of a (NHC)Ru‐supported PAF
supports due to their better performance towards the metal catalysts (PAF‐(NHC)Ru) as brown solids containing about 0.2
functionalization than PAFAd materials.
mmol/g of Ru (ICP‐AES) (Table S2). The comparison of
elemental analysis and FTIR data indicated that only a part of
imidazolium groups anchored on the polymeric supports took
part in the reactions with the metal (Ir or Ru) to form the
corresponding metal‐carbene complexes (Table S2, Figure S1‐
S2).
Cl
R
r
I
N
N
]
)
d
o
c
(
)
c
a
c
a
(
r
I
13C CP‐MAS NMR spectra of resulting NHC‐complexes
displayed signals corresponding to aromatic carbons between
[
n
PAF-(NHC)Ir: PAF-IMesIr, PAF-IPyIrr
R
N
120 and 160 ppm, ‐CH3 group of mesityl moiety at
The metalation could be also confirmed by a weak peak for
NCN carbon36,43 at
176 ppm for iridium and at 191 ppm for
∼20 ppm.
N
Cl
1
.-
C
Cl
Cl
∼
K
[(
C
H3
)
3S
i
]
2N
2
.
R
-
[
R
u
ruthenium complexes (Figures S3a‐i).
l2
PAF-Im
(
Ru
p
-
c
y
m
e
n
e
)]2
N
The thermal stability of the supported catalysts was estimated
using TG analysis. TGA curves are shown in figures S4a‐d. The
TGA curves of these catalysts are similar showing one
important weight loss at c.a. 400 oC.
N
R:
R:
Im: I M e s
Im:IPy
n
N
Field emission scanning electron microscopy (FE‐SEM) showed
no morphological changes in PAFs derivatives, PAF‐CH2Cl, PAF‐
Im and PAF‐(NHC)M, which confirms that the shape of the
materials remained intact (Figure S5a‐b). PAF‐(NHC)M are
robust and stable complexes and their X‐ray powder
diffraction analyses revealed that these PAFs are amorphous
solids (Figure S6). N2 adsorption‐desorption isotherms at 77 K
PAF-(NHC)Ru: PAF-IMesRu, PAF-IPyIr
Scheme 2. Preparation of PAF‐(NHC)M (M: Ir, Ru).
PAF‐(NHC)Ir were prepared by reaction of the respective PAF‐
imidazolium salts and [Ir(acac)(cod)]36 in dichloromethane at
40 oC (Scheme 2). The resulting PAF‐(cod)(NHC)IrX‐compounds
were filtered, and washed thoroughly with dichloromethane.
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are shown in Figures S7a‐g in the supporting information with out in the presence of KOH (Table S3, entries 2‐5). Generally,
View Article Online
DOI: 10.1039/C6CY00597G
BET specific surface area values of 383 m²/g for PAFspf‐IPyIr the imine formation readily proceeds upon heating. The
and 279 m²/g for PAFC‐IPyRu; IMes derivatives have lower BET reaction was also performed in the absence of the catalyst to
values.
estimate the contribution of PAF‐(NHC)M‐catalyst to imine
formation, and this was not reached to obtain neither amine
nor imine (Table 1, entry 12). For comparison purposes the
reaction was also tested in the presence of Ir(IPy)(cod)Cl (as
homogeneous reference catalyst), and we found a lesser
activity and selectivity than the corresponding supported PAF
catalyst (Table 1, entry 11). Comparing the structure of parent
PAF‐supports we also observed that spirobifluorene‐
derivatives resulted better catalysts that tetraphenylmethane‐
ones (see table 1). By tracing the reactions by using GC‐MS,
Catalytic activity
N‐alkylation of amines with alcohols.
The environmentally‐benign N‐alkylation of primary amines
with alcohols as alkylating reagents in the presence of
transition metal catalysts37 is important because secondary
amines have widely been used as synthetic intermediates for
pharmaceuticals, agrochemicals, bioactive compounds,
polymers, and dyes.38,39 The reaction is atom economical and
the only reaction byproduct is water. Typically, iridium or
ruthenium‐catalyzed N‐alkylation of amines and amides has
become a useful way to achieve versatile amine and amide
derivatives using alcohols as the greener alkylating reagents.40
This strategy takes the hydrogen from the alcohol to form an
aldehyde which can react with an amine to form an imine, and
the hydrogen is then used to give a C‐N bond.41 The N‐
alkylation has been mainly studied with soluble homogeneous
transition metals37i,42 This prompted us to test the catalytic
activities of new heterogenized‐PAFs‐(NHC)iridium and
ruthenium complexes for N‐alkylation of amines with alcohols.
As a model, we studied the reaction of aniline with benzyl
alcohol in toluene in the presence of 0.5 mol% of catalyst and
KOH as base at 130 oC for 24 h; the reaction can be performed
with a variety of different bases without large variations in
reactivity. The results are summarized in Tables 1 and S3.
amine was observed as the major product in all of the PAFs
‐
(NHC)Ir‐catalyzed‐reactions. Reactions follow the general
accepted reaction pathways where the intermediate aldehyde
stays coordinated to the Ir‐complex and reacts with the amine
to give the hemiaminal which is also bound to the catalyst;
dehydration to the imine and reduction to the product amine
would also takes place without breaking the coordination to
the catalyst, as it has been previously proposed.43 In the case
of PAFs‐(NHC)Ru‐catalysts last reduction step don’t takes place
and mainly lead to the imine products.
For preparative purposes, an experiment between aniline and
benzyl alcohol was scaled up by a factor of 10 and a conversion
of 100% and a selectivity of 50% towards the amine were
reached at 24 h; being necessary additional 48 h to obtain a
80% selectivity.
The scope of the PAFspf‐IPyIr‐catalyzed N‐alkylation was
examined after optimization of the reaction conditions (Table
2). Various amines and alcohols were then chosen to explore
the activity and all reactions efficiently proceeded to give the
corresponding secondary amines in moderate to excellent
yields.
Table 1. Effect of support and metal on the alkylation of anilines with benzyl alcohol
using PAFs‐(NHC)M.a
Table 2. Effect of substrates on the alkylation of anilines with benzyl alcohols using
PAFspf‐IPyIr.a
Yieldb
Selec. [%]
entry
catalyst
R
[%]
100
100
100
100
91.7
100
100
95.1
100
100
74.7
10
A
B
1
2
3
4
5
6
7
8
9
PAFspf‐IPyIr
PAFspf‐IPyIr
PAFspf‐IPyIr
PAFspf‐IMesIr
PAFspf‐IMesRu
PAFc‐IPyIr
PAFc‐IPyRu
PAFc‐IPyRu
PAFc‐IMesIr
PAFc‐IMesRu
Ir(IPy)(cod)Cl
none
H
OCH3
CH3
H
H
H
CH3
OCH3
H
H
H
4.1
6.0
95.9
94.0
80.0
85.9
66.2
77.9
2.0
20.0
14.1
33.8
22.1
98.0
92.5
20.8
94.3
52.8
10
Selec. [%]
entry
R
R1
A
B
1
2
3
4
5
6
7
8
H
OCH3
Cl
CH3
Br
H
H
H
H
H
H
H
H
OCH3
CH3
Cl
4.1
6.0
95.9
94.0
85.3
80.0
14.7
20.0
59.9
30.4
26.6
21.9c
7.5
79.2
5.7
b
‐
10
11
12
69.6
68.3
55.2b
47.2
‐
H
aReaction conditions: aniline (0.104 mmol), benzyl alcohol (0.208 mmol), KOH
(0.13 mmol), toluene (0.3 mL), 130 oC, 24 h, 0.5 mol % catalyst based on metal.
bDetermined by GC and GC‐MS.
aReaction conditions: aniline (0.104 mmol), benzyl alcohol (0.208 mmol), KOH
(0.13 mmol), 0.5 mol % based on iridium, toluene (0.3 mL), 130 °C, 24 h, 100%
yield was determined via GC and GC‐MS. bN‐benzylaniline. cN‐benzylideneaniline.
When the reaction was carried out without a base, only imine
was formed (Table S3, entry 1) and N‐benzylaniline was
obtained in an excellent yield when the reaction was carried
First, different amines were studied in the reaction with benzyl
alcohol; p‐substituted anilines with methyl, methoxy, and
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chloro substituents participated in an efficient way in the Transfer Hydrogenation Catalysis.
View Article Online
DOI: 10.1039/C6CY00597G
secondary amines formation (entries 1‐4). p‐bromoaniline was
Catalytic transfer hydrogenation is one of the most important
applications of (NHC)‐Ir(I) and Ru(II) complexes.36,44 In this
work, the reduction of acetophenone to 1‐phenylethanol, with
isopropanol as hydrogen donor in the presence of KOtBu as
the base, was chosen as a model reaction to test the
performance of PAFs‐(NHC)Ir and Ru as catalysts for transfer
hydrogen reactions. Several catalytic runs have been carried
out at different catalyst concentrations using 0.5, 1.0, 2.0, 2.5
mol%. The catalytic activity of PAFs‐(NHC)iridium was similar
to that of the comparable ruthenium catalyst (Table 4), several
bases were also employed being KOtBu the most effective.
a poor substrate due to considerable dehalogenation as a side
reaction (entry 5). p‐Methoxy and p‐methyl substituted benzyl
alcohols (entries 6 and 7) reacted well with aniline to lead the
corresponding amine and p‐chloro substituents reacted with
good yields although dehalogenation also occurs (entry 8). An
experiment with four times of reactants and catalyst was also
performed and reaction was completed in 24 h.
In organic synthesis, there are many advantages of replacing
organic solvents with water (an inexpensive, safe and
environmentally friendly solvent); in this context, the
development of water‐tolerant catalysts has become an active
area of research. We studied the efficiency of PAF‐system for
the N‐alkylation of amines with a benzyl alcohol in water under
air. The results are summarized in Table 3. The reaction
proceeds smoothly using water as solvent with KOH as base
(table S5) and resulted in the selective formation of N‐
benzylideneanilines, except when p‐anisidine was the
substrate (Table 3, entry 4). In addition, the reuse of the
water‐tolerant PAF‐(NHC)Ir catalyst has also been
demonstrated (Table S6).
Table 4. Catalytic hydrogen transfer from 2‐Propanol to acetophenone using PAFs‐
(NHC)Ir and PAFs‐(NHC)Ru.a
entry
catalyst
catalystb [mol %]
yieldc [%]
TONd
1
2
3
4
5
6
7
8
9
10
11
12
13
14
PAFspf‐IPyIr
PAFspf‐IPyIr
PAFspf‐IPyIr
PAFspf‐IMesIr
PAFc‐IPyIr
PAFc‐IMesIr
PAFc‐IMesIr
PAFc‐IMesRu
PAFc‐IMesRu
PAFc‐IPyRu
PAFc‐IPyRu
PAFc‐IPyRu
IPyRu
2.5
1.0
0.5
0.5
0.5
0.5
5.0
5.0
2.5
2.5
2.0
0.5
2.0
5.0
94.6
99.0
85.0
69.1
41.6
42.3
98.2
98.7
49.7
99.0
92.0
53.0
94.6
2.0
37.8
99.0
170.0
138.2
83.2
84.6
19.6
19.7
19.9
39.6
46.0
106
Table 3. Alkylation of anilines with benzyl alcohol using PAFc‐IMesIr in water.a
Selec. [%]
entry
R
Conv. (%)c
A
B
5.0
‐
1
2
3
4
H
CH3
Cl
67.5
91.3
95.6
100
94.9
100
100
62.3
‐
47.3
‐
OCH3
37.7
PAFc‐IPyCl
aReaction conditions: aniline (0.104 mmol), benzyl alcohol (0.208 mmol), 3.0
mol% catalyst based on iridium, KOH (0.13 mmol), water (0.3 mL), 100 °C, 24h.
Yields determined by GC and GC‐MS. dTON: [conv.]/[cat] (for a single run)..
aReaction conditions: acetophenone (0.043 mmol), KOtBu (0.12 mmol, iPrOH (0.5
mL), 82 oC, 24 h. bBased on Metal. cYields determined via GC and GC‐MS. dTON is
defined as [1‐phenylethanol]/[cat] (for a single catalysis run).
Recycling of PAFspf‐IPyIr was carried out for the N‐alkylation of
The scope of the reaction was studied with different ketones in
the presence of PAFC‐IPyRu or PAFspf‐IPyIr catalysts, KOtBu as
p‐methoxyaniline with benzyl alcohol finding that the activity
was maintained for at least eight cycles although selectivity to
the imine decreased after the fifth run (Figure S8). In order to
verify whether the observed catalysis is derived from solid
the base, and iPrOH as the solvent as well as hydrogen source,
as shown in Table 5. Benzophenone and p‐
chloroacetophenone exhibited almost quantitative yields at
the S/C ratio of 50. The position of substitution on the phenyl
ring of aniline affected to the reaction yield. Interestingly,
moderately activating groups i.e. methyl at the o‐position
furnished higher yield compared to the para position.
PAFspf‐IPyIr or leached iridium species, the N‐alkylation of
aniline with benzylic alcohol was carried out and the Ir‐catalyst
was removed from the reaction mixture by filtration at ca. 40%
conversion of aniline. After removal of the catalyst, the
reaction was again carried out with the filtrate under the same
conditions. In this case, the reaction was stopped. It was
confirmed by ICP‐AES analysis that no iridium was detected in
the filtrate (below detection limit). All these facts can rule out
any contribution to the observed catalysis from iridium species
that leached into the reaction solution and the observed
catalysis is intrinsically heterogeneous. Analysis for the
recovered catalyst shows that the structure was maintained
without important degradation (see ESI).
After the end of reaction PAFC‐IPyRu was filtered and recycled
at least six runs without loss of reactivity (Figure S9).
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Table 5. PAFC‐IPyRu‐catalyzed hydrogen transfer from 2‐Propanol to ketones.a
several times with dichloromethane and THF until the filtrate
View Article Online
was colorless and finally dried under DvOaIc: u10u.1m039(/9C56C%Y0).05T9h7Ge
ruthenium amount was found to be 0.10‐0.20 mmol/g based
on ICP‐AES analysis.
Catalytic activity
entry
Ketone
Yieldc [%]
PAFspf‐IPyIr
N‐alkylation of amines with alcohols. Alcohol (1.5 mmol) and
amine (1.0 mmol), were weighed into a micro reactor vessel.
KOH (8 mg, 0.13 mmol) was added, followed by solvent (0.30
mL). The mixture was put under an atmosphere of nitrogen,
and catalyst (2.70 mg, Ir: 0.5 mol%) was added before
stoppering the flask and immersing it in a preheated oil bath
(130 oC) for 24 h. The reaction mixture was cooled and filtered.
Aliquots were analyzed by GC‐MS.
PAFc‐IPyRu
92.0
1
2
3
4
H
4‐Cl
2‐CH3
4‐CH3
99.0
98.6
99.2
94.0
95.8
99.0
93.0
aReaction conditions: ketone (0.043 mmol), KOtBu (0.12 mmol, iPrOH (0.5 mL), 82
°C, 2.0 mol% catalyst (based on Ru), 24 h. cYields determined via GC and GC‐MS..
Hydrogen transfer from 2‐Propanol to ketones. Ketone (1.0
mmol), KOtBu (4.0 mmol), catalyst (3.68 mg, Ru: 2.0 mol%) and
iPrOH (0.5 mL) were added to a micro reactor vessel, and the
mixture was refluxed for 24 h. The reaction was cooled, and an
aliquot was filtered and analyzed by GC‐MS.
Recycling experiments. According to the general procedure for
the N‐alkylation of amines with alcohols or transfer hydrogen
reactions, the first run reaction was carried out. After
completion of the reaction, the catalyst was filtered off,
washed with CH2Cl2, and then vacuum‐dried. The recovered
catalyst was used for consecutive reactions under the same
conditions.
Conclusions
This paper demonstrates that polymeric aromatic frameworks
are easily obtained with high physicochemical stability and can
be used as supports to obtain robust heterogenized catalysts.
Here, we have shown that N‐heterocyclic carbene complexes
can be supported onto PAFs maintaining the integrity of both
the organometallic moiety and the organic support. These
catalysts were superior to iridium catalyzed homogeneous
system for the transfer hydrogen reactions and N‐alkylation of
amines with alcohols in the same conditions. The catalyst
could be recovered by simple filtration and reused without
significant loss of its catalytic activity. These unique
characteristics clearly indicate that PAF catalysts based on
covalently and homogeneously active sites could provide new
potential in the exploration of heterogeneous catalysts and
their applications in sustainable catalysis.
Acknowledgements
This work was supported by MINECO through the Consolider
Ingenio 2009 (CSD‐0050, MULTICAT), MAT2014‐52085‐C2‐2‐P
projects. A.M.R.A. thanks MINECO for financial support.
Experimental
Notes and references
A
detailed synthesis for parent PAFs materials and
postfuncionalized materials PAF‐CH2Cl and PAF‐Im was
described in supplementary material.
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DOI: 10.1039/C6CY00597G
Polymeric aromatic frameworks (PAFs), easily obtained from organic platforms, result excellent
supports to yield robust well-defined organometallic heterogenized catalysts.
1