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“Release and catch” catalytic systems

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Cite this: Green Chem., 2013, 15, 2608 Michelangelo Gruttadauria,* Francesco Giacalone and Renato Noto

Received 12th June 2013,
Accepted 23rd July 2013
DOI: 10.1039/c3gc41132j
www.rsc.org/greenchem
In this perspective article the “release and catch” catalytic system concept is discussed. A “release and
catch” catalytic system is prepared by non-covalent immobilization of the catalytic moiety on a suitable
support, but differently from the usual non-covalently supported catalyst, the catalytic moiety is released
in solution over the course of the reaction and it is recaptured at the end of the reaction. Such a “cata-
lyst-sponge like” or “boomerang” system allows one to combine the benefits of homogeneous and
heterogeneous catalysis and can be applied to organometallic-based catalysts, organocatalysts and
metal-based catalysts.

Introduction Further drawbacks of homogeneous catalysis are the high

Recovery and reuse of catalytic systems is a key issue in
modern chemistry.1–4 Homogeneous catalysis facilitates a high
degree of tunability of the catalyst activity, chemoselectivity,
regioselectivity and enantioselectivity.5–7 However, the need for
an additional separation step, such as distillation, extraction
and chromatography, required to remove the homogeneous
catalyst from the product mixture coupled with the lack of
efficient recycling methodologies may restrict the use of homo-
geneous catalysis to the production of valuable fine chemicals.
Dipartimento di Scienze e Tecnologie Biologiche, Chimiche e Farmaceutiche
(STEBICEF), sez. di Chimica, Viale delle scienze Ed. 17, 90128 Palermo, Italy.
E-mail: michelangelo.gruttadauria@unipa.it; Fax: +39 091 596825;
Tel: +39 091 23897534
prices of metal complexes and the leaching of metal ions
which causes the often laborious removal of metals from reac-
tion mixtures.8–10 In the case of homogeneous organocatalytic
reactions, a major drawback is the high catalyst loading
(10–20 mol% in many cases). These aspects make compulsory
a good recovery of the catalyst, especially for highly expensive
molecules.11
Heterogeneous supports allow efficient recycling by fil-
tration. The ideal heterogeneous catalytic system will maintain
the catalytic efficiency of the homogeneous counterpart and
will be indefinitely recovered and reused without any loss in
activity. In the real cases a substantial decrease in catalytic
activity and/or enantioselectivity of the immobilized catalysts
is frequently observed because of restriction of the solid
matrix, which limits mobility and accessibility of the active

Michelangelo Gruttadauria is a Francesco Giacalon is an assist-

Full Professor of Organic Chem-
istry at the University of
Palermo. His fields of interest
have previously included hetero-
cycle synthesis, physical organic
chemistry, and stereoselective
synthesis using organoselenium
chemistry and chiral allyl stan-
nanes (with Prof. E. J. Thomas).
His current interests include
organocatalysis (he is in the MC
Michelangelo Gruttadauria of COST Action CM905-ORCA)
and new supported recyclable
catalysts. He is the author of over ninety papers and reviews, and
book chapters and the co-editor of the book “Catalytic Methods in
Asymmetric Synthesis” published by Wiley in 2011.
ant professor at the University of
Palermo. He received his Ph.D.
from the University Complutense
of Madrid (UCM) in 2004, under
the guidance of Prof. N. Martín
and Prof. J. L. Segura. Since Sep-
tember 2004 he worked at the
UCM as a European Science
Foundation postdoc-Fellow in
the field of molecular electronics.
From 06/2005 to 01/2011 he was
Francesco Giacalon a postdoc researcher at the
Organic Chemistry Department
of the University of Palermo. He is the co-editor of the book
“Catalytic Methods in Asymmetric Synthesis” published by Wiley
in 2011.

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sites after several cycles.12–16 In the latter event, a possible
regeneration of the catalytic system could restore the original
catalytic activity, although this process represents an
additional cost. In contrast, the whole catalytic system
(support–catalyst) is lost whenever the catalytic activity cannot
be restored.
Several strategies for catalyst recycling have been explored.
First, the active catalyst can be covalently linked to some kind
of support. Such supports can be insoluble or soluble. The
main advantage of covalently linked insoluble catalysts is their
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easy recovery whereas soluble supported catalysts have the
main disadvantage of being recovered after precipitation,
which could be non-quantitative. On the other hand, soluble
supported catalysts and tagged catalysts could provide higher
levels of activity or enantioselectivity owing to their ability to
mimic the activity and stereoselectivity of the corresponding
unsupported catalysts. In addition, soluble supported catalysts
are easily characterized using standard techniques whereas
polymer-supported insoluble catalysts need more complex
technologies for their characterization. Various scaffolds have
been used, such as dendritic,17–20 polymeric organic,14
inorganic,21–23 or hybrid supports.24–26 A particular class of
soluble/insoluble catalysts are thermomorphic catalytic
systems.27,28 Another recent class is constituted by self-sup-
ported catalysts which are infinitely extended functional
metal–organic assemblies generally constructed by the cross-
linking of polytopic ligands and metal centers via coordination
bonds.29
A second type of recycling methodology is biphasic cataly-
sis: the selective partitioning of the catalyst from the reactants
and products that can be achieved by employing two immisci-
ble solvents in the separation step. The most employed bi-
phasic systems are supported aqueous phase catalysis,30
fluorous biphasic catalysis,31,32 (supported) ionic liquids33,34
and supercritical fluids.35–37 An industrial application of this
Renato Noto obtained a Chem-
istry degree at the University of
Palermo in 1970. He has been,
since 1990, a Full Professor of
Organic Chemistry. He began
research activity in the field of
Physical Organic Chemistry with
Professor Domenico Spinelli.
Successively, his interest has
been directed to stereocontrolled
synthesis of functionalized
heterocyclic rings and to studies
Renato Noto on inclusion equilibria of aro-
matic molecules in cyclodextrins.
Recently he focused his attention on the behavior of organic salts
as ionic liquids and/or gelators. He is the author of about 150
publications and 4 reviews.
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Fig. 1 Release and catch catalytic system.
approach is the biphasic Ruhrchemie/Rhône-Poulenc process
for the hydroformylation of propene.38
The third type of recovering strategy is the use of non-
covalently supported catalysts.39,40 The catalyst can be adsorbed,
dissolved, included or linked by electrostatic interactions in
several supports. Interestingly, if after some re-use the catalytic
system shows lower catalytic efficiency, the spent catalyst can be
removed and the support can be recovered and re-charged with
fresh catalyst. The disadvantage of this approach is that the cat-
alytic system works in a heterogeneous manner.
An improvement of the latter strategy is the development of
a “release and catch” or “boomerang” catalytic system. A
“release and catch” catalytic system is prepared by non-
covalent immobilization of the catalytic moiety on a suitable
support, but differently from the usual non-covalently sup-
ported catalyst, the catalytic moiety is released in solution
during the course of the reaction and it is recaptured at the
end of the reaction. Such a “catalyst-sponge like” system allows
one to combine the benefits of homogeneous (high catalytic
activity and enantioselectivity, for chiral catalysts) and hetero-
geneous catalysis (easy separation and recycling) (Fig. 1).
Despite such benefits, this strategy is yet to be widely inves-
tigated and employed. In our opinion this methodology
deserves more attention. Here we would like to highlight
several examples reported in the literature in order to show the
potentiality of this methodology. These examples are not
restricted to a particular field but consider organometallic-
based catalysts, organocatalysts and metal-based catalysts.
Moreover, different technologies (batchwise reactions, flow
reactions and reverse-flow adsorption), supports (i.e., carbon
nanotubes, silica, alumina, supported ionic liquids) as well as
different kinds of molecular recognition (π–π stacking, hydro-
gen bonding, etc.) can be employed.
“Release and catch” catalytic systems
Carbon nanotubes (CNTs) have attracted attention because of
their mechanical, electronic and chemical stability properties
and some examples have been reported on their use as a
support for covalently linked catalysts.41–43 On the other hand,
CNTs can be also employed as a support for non-covalently
linked catalysts which can be released and recaptured during
the reaction. To do this, the catalytic moiety can be connected
to a polyaromatic ring, which can be adsorbed on the surface
of CNTs via π–π stacking (Scheme 1).
An example of this approach is the use of pyrene-modified
catalysts. The complex of Rh(I) with pyrene-modified pyrphos
ligand (R,R-1) (Scheme 2) was found to be strongly adsorbed
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Scheme 1 Release and catch catalytic system based on CNTs/pyrene-tagged
catalysts.
Scheme 2 Asymmetric hydrogenation of α-dehydroamino esters.
on CNTs in EtOAc and weakly adsorbed on CH2Cl2.44 The cata-
lyst (R,R-1) was used in the asymmetric hydrogenation of
α-dehydroamino esters (Scheme 2). Reactions were carried out
in CH2Cl2 in the presence of CNTs. At the end of the reaction,
solvent was removed under reduced pressure and EtOAc was
added. The catalyst was adsorbed on CNTs and recovered by
filtration and directly used for the next cycle. After 9 cycles
conversion was maintained, even if the reaction time was
gradually increased. However, in the 10th cycle a dramatic
drop in activity was observed.
The pyrene-tagged ruthenium carbene 2 (Scheme 3) was
immobilized on CNTs by sonication in dichloromethane
Scheme 3 Ring closing metathesis reactions.
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solution.45 A loading of about 1.5 mg of 2 for 10 mg of CNTs
was obtained. The desorption of 2 was found to be greatly
affected by the reaction temperature and solvent polarity. Sig-
nificant amounts of 2 were desorbed by nonpolar solvents, such
as benzene and toluene, and by polar solvents, such as dichloro-
methane and tetrahydrofuran. When a polar solvent, such as
ethyl acetate or acetone, was used, only a small amount of 2 was
desorbed. Moreover, the temperature affected the amount of
desorbed catalyst. In acetone at 0 °C or 25 °C no detectable
amount of 2 was observed, whereas about 7% was desorbed at
35 °C and 80% was desorbed at 56 °C after 24 h.
The catalytic system was applied to a variety of ring-closing
metathesis reactions that led to various carbocyclic com-
pounds as well as nitrogen- and oxygen-containing hetero-
cycles. Reactions were carried out in acetone at 35 °C or 56 °C.
At the end of the reaction, the solution was concentrated and
stirred at 0 °C allowing the desorbed catalyst to be re-immobi-
lized on CNTs. Then, the catalytic material was separated by
centrifugation and used for another cycle. In this study, one of
the aspects of the strategy based on the non-covalently
attached catalysts was also highlighted: the recovery and reuse
of the support when the entire catalytic system is not working
anymore. Diene 3 was used in 8 consecutive cycles in the pres-
ence of catalyst 2 (Scheme 3). In the 8th cycle a drop in activity
was observed, and then, the catalyst was removed and the
support was re-employed. This approach was repeated six
times.
A pyrene-tagged palladium NHC complex 4 was immobi-
lized on highly magnetic graphene-coated nanoparticles
through π–π staking interactions (Scheme 4).46 The Pd-
complex was used in the hydroxycarbonylation of aryl halides
in water under atmospheric pressure of CO. The complex dis-
sociated from the nanoparticles during the course of the reac-
tion in water at 100 °C, and was recaptured on the graphene
layer at room temperature. Six different substrates were
employed and, in total, 16 cycles were carried out. After each
cycle, the catalytic material was recovered by magnetic decan-
tation. The catalyst loading was 0.1 mmol g−1 and inductively
coupled plasma atomic emission spectroscopy (ICP-AES)
measurements indicated that 63% of the Pd-complex was de-
sorbed from 5 after filtration using boiling water.
The pyrene-tagged gold(I) complex 6 immobilized in CNTs
(Scheme 5) was employed in the cyclization of enynes and
propargylic carbonates.47
Scheme 4 Hydroxycarbonylation of aryl halides.
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Scheme 5 Cyclization of enyne.
A comparison between unsupported 6 and CNTs-supported
6 indicated no difference in catalytic activity. Such a result
prompted authors to the recycling study of the catalytic
system. This investigation was done using enyne 7 in dichloro-
methane at room temperature for 30 min. Then, the reaction
mixture was cooled to −40 °C and centrifuged to recover the
catalytic system which was ready for the new run. In dichloro-
methane, catalyst 6 is released, and then, it is re-captured fol-
lowing a lowering of the temperature. In the first four cycles,
enyne 7 was quantitatively transformed into products 8 and 9
(ratio 8 : 9 = 88 : 12). Loss in activity was observed during cycles
5 and 6 (Scheme 5). A recycling study using a different enyne
showed a constant decrease in activity. Leaching of the catalyst
upon recycling was demonstrated, although the leaching
seems rather low to fully explain the loss in activity.
When a non-covalently supported catalyst is employed, it is
believed that only batch conditions can be used. This is not
true. The “release and catch” catalytic system can be coupled
with flow systems. An interesting concept for the recovery and
recycling of homogeneous catalysts is based on the reverse-
flow adsorption48,49 (RFA) which combines adsorptive sepa-
ration with reverse flow technology. It is essential that adsorp-
tion is reversible to allow desorption of the catalyst system and
reintroduce it into the reactor with the reactor feed (Fig. 2).
An example based on the use of pyrene-tagged catalysts and
CNTs as supports is the following.50 Palladium NHC com-
plexes 10 and 11 (Scheme 6) were loaded on CNT columns
using DMF as the loading solvent at room temperature. UV
spectra of the filtrate during the loading phase revealed no evi-
dence of 10 or 11, indicating that 100% of the complexes were
captured. The column temperature was raised to 100 °C, and
10 and 11 were eluted with DMF. It was observed that the
single-pyrene complex 10 binds less strongly than the double-
pyrene complex 11. Then, a “release and catch” catalytic flow
system was installed (Scheme 6). The process is characterized
by: (a) a release column, (b) a reactor segment, and (c) a
capture column. Such a system was used for Suzuki and Heck
coupling reactions. The Pd cross-coupling experiments were
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Fig. 2 Reverse-flow adsorption (RFA). The substrate is pumped into the reactor
through path A and desorbs the catalyst from bed 1 until bed 2 is saturated.
Then the flow is reversed and the substrate is pumped in through route B.
Scheme 6 Release and catch continuous flow Suzuki reaction under RFA con-
ditions catalyzed by 10 or 11.
initiated by first adsorbing 10 or 11 on the CNT release
column. The reaction was started by heating the release
column to 100 °C and the reactor coil to 60 °C, as well as
placing a cooling bath (4 °C) on the output of the reactor coil.
The Suzuki reaction was carried out by injecting PhI, PhB-
(OH)2, and aq. TBAOH as a 0.1 M solution in DMF into the
release stream at a flow rate of 50 or 25 μL min−1. After the
first cycle, the system was reversed, and a second reaction
cycle was performed. The Suzuki reaction was successful using
both catalysts 10 and 11. Complex 11 exhibited the best overall
performance using a 30 min residence time. Catalyst 11 pro-
vided 99% conversion with no detectable leaching in the
forward direction, and 99% conversion with 21% leaching in
the reverse reaction. The leaching observed for 11 in the
reverse reaction might be due to competition between 1,1′-
biphenyl product and 11 for CNT binding sites. The same
approach was used for the Heck reaction. Both catalysts gave
high yields in the forward and reverse directions. Less leaching
was observed using the single-pyrene complex 10.
The RFA approach can be based on other substrate–support
interactions. The support (adsorbent) can be functionalized
with a well-defined binding motif, and the complementary
motif is covalently attached to the ligand (substrate). This
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Fig. 3 One-step simultaneous adsorption of the catalyst (metal–ligand
complex) and excess ligand on the adsorbent material.
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supramolecular anchor enables a one-step simultaneous
adsorption of the catalyst (metal–ligand complex) and excess
ligand on the adsorbent material (Fig. 3). The use of such a
non-covalent, supramolecular host–guest anchoring strategy
for the immobilization of homogeneous catalysts was pre-
viously investigated and allowed a sufficiently strong catalyst
immobilization and an efficient catalyst recycling.51 This
approach was further developed for the recycling of homo-
geneous rhodium-based catalysts through the RFA
methodology.52
In order to develop such a methodology, the silica gel
adsorbent 12 was synthesized. Besides, the complex [Rh(cod)-
(13)]BF4 was prepared by mixing [Rh(cod)2]BF4 and ligand 13
(Scheme 7). A solution of the complex was pumped with a flow
rate of 0.1 mL min−1 from the reactor through the adsorption
bed loaded with 12 (0.5 g, 1 mL volume) and collected at the
exit of the bed (Fig. 4). The formation of the supramolecular
structure 14 (Scheme 7) was due to (a) an ionic interaction
between the carboxyl group of the guest tail and the tertiary
amine of the host, and (b) hydrogen-bonding interactions
between urea groups on both host and guest molecules. After
20 min the flow was reversed, and fresh solvent was pumped at
the same flow rate into the bed from the opposite side to
desorb the metal complex into the reactor (Fig. 4). The direc-
tion of flow was reversed every 20 min and the metal complex
Scheme 7 Non-covalently functionalized silica material.
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Fig. 4 RFA based on silica 12 and the complex [Rh(cod)(13)]BF4 to give 14.
was adsorbed and desorbed up to five times. After the five
adsorption–desorption experiments the rhodium complex was
distributed over the reactor and the bed, with 40% of the
rhodium in the reactor and the remainder on the silica bed.
The catalytic system was used for the asymmetric hydrogen-
ation of methyl acetoamidoacrylate (MAA) (Scheme 8) and for
the asymmetric hydrosilylation of acetophenone (Scheme 9).
In the case of hydrogenation of MAA, after the formation of
the complex, the system was purged with H2 and the substrate
was added. The conversion dropped significantly from 55.3 to
26.2% after eight consecutive runs, whereas selectivity
remained in the range of 18–16%.
Moreover, catalyst leaching at the exit of the adsorption
beds was found to be around 15% of the total amount of
rhodium added into the system. This indicated that the pres-
ence of the substrate and products in solution influenced to
some extent the adsorption of the rhodium complex to the
silica support. In the case of the hydrosilylation of acetophe-
none, the catalytic performance of [Rh(cod)(13)]BF4 remained
stable for up to eight consecutive runs, with comparable activi-
ties and selectivities in each cycle (Scheme 9).
In the above non-optimized system, a large part of the cata-
lyst resided on the adsorption bed and was therefore not used.
Further studies and a significant investment are needed for
the large scale implementation of this concept. Then, authors
Scheme 8 Asymmetric hydrogenation of methyl acetoamidoacrylate catalyzed
by material 14 under RFA conditions (Fig. 4).
Scheme 9 Asymmetric hydrosilylation of acetophenone catalyzed by material
14 under RFA conditions (Fig. 4).
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Fig. 5 Catalyst recycling via a reversible catalyst adsorption strategy using non-
covalent interactions. Reproduced from ref. 53.
have studied similar adsorption strategies for batchwise reac-
tions (Fig. 5).53
The concept is displayed in Fig. 5. After a batch reaction the
catalyst is selectively scavenged by the tailor-made support
using non-covalent binding. The catalyst is separated from the
product mixture, and the adsorption bed is washed with a
different (more polar) solvent to disrupt the supramolecular
interactions, thus releasing the catalyst from the bed. Reintro-
duction of the catalyst into the reactor and addition of new
reactants allows the subsequent catalytic run with the recycled
active catalyst. This methodology was employed in the homo-
geneous hydroformylation of 1-octene using a Rh-catalyst
tethered with a support-specific binding motif (Scheme 10).
Various commercially available supports were explored,
with the end-capped silica-alumina showing the best results
with respect to ligand-adsorbing properties. Optimization
experiments revealed that an additional equivalent ligand
must be added in each batch reaction. Four successful re-
cycling experiments were performed where the catalyst was
taken out of the reactor, passed over an adsorption bed and
reintroduced into the reactor. The activity dropped slightly in
the second run but remained stable until the fifth run. The
selectivity was retained in the first four reactions, but was
Scheme 10 Rhodium catalyzed hydroformylation of 1-octene.
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Scheme 11 Molecular recognition between the support and the metal ligand
based on hydrogen bonding.
almost completely lost in the fifth run. Rhodium analysis
showed that a significant amount of rhodium still resided on
the catalyst scavenger bed.
A different approach for the recycling of catalysts is based
on the establishment of hydrogen bonding between the
support and the catalytic moiety (Scheme 11). In this case a
copper(I)-based catalyst having a ligand (15) equipped with an
affinity tag was isolated from a crude reaction mixture on the
basis of quadruple hydrogen-bonding interactions using a
resin (16) functionalized with a complementary affinity tag.
The catalyst was applied in a homogeneous catalytic reaction
in an organic solvent, assuming that the affinity tag does not
affect its catalytic activity. When the reaction was complete the
solvent was evaporated and the residue was taken up in CHCl3,
and resin 16 was added. After filtration, the product was iso-
lated from the filtrate and the resin was transferred to a
mixture of DMF and methanol to cleave the hydrogen bonds.
After filtering off the resin, the filtrate was concentrated and
the crude catalyst was used in the next reaction without
further purification.54
The catalytic system was tested in the synthesis of 2-aryl-
benzo[b]furans and in the [3 + 2] Huisgen cycloaddition
(Scheme 12).
Further examples of “release and catch” catalytic systems
are based on the use of ionic liquids (ILs). A major limitation
of traditional biphasic ionic liquid–organic systems is the
need of relatively large amounts of ILs, which are still expen-
sive solvents. In addition, the high viscosity of ILs compared
to classical organic solvents can induce mass transfer limit-
ations. Both these drawbacks can be circumvented by immobi-
lizing a thin film of ionic liquid onto a high surface area
support. The supported ionic liquid phase (SILP) approach
involves the presence of a support material that is modified
with adsorbed layers of ionic liquid serving as the reaction
phase in which the homogeneous catalyst is confined.34,55
Scheme 12 Cu-catalyzed [3 + 2] Huisgen cycloaddition performed with the
release and catch system 15/16/[Cu(PPh3)]Br.
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Fig. 6 The release and catch catalytic system based on imidazolium-modified

supports and catalysts.
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A modification of this approach involves the use of covalently

attached ionic liquid moieties.56 On such a kind of support a Scheme 13 Asymmetric aldol reactions catalyzed by material 19.

homogeneous catalyst may be adsorbed, and the use of the

whole system is based on the desorption–adsorption route regenerated sample of 19 which was then subjected to a longer
during the reaction and work-up steps. Initially, the catalyst is series of recycling experiments (15 cycles) (Scheme 13).
adsorbed on the surface of an imidazolium-modified silica gel With the aim to increase the affinity of a nitroxide catalyst
support (Fig. 6). In order to increase the affinity between the towards an imidazolium-modified silica gel (20), a bis-imida-
surface of the imidazolium-modified silica gel and the catalyst, zolium tag was introduced in the 4-hydroxy-TEMPO (catalysts
the latter is also modified with an imidazolium tag. During 21a and 21b) (Fig. 7). In addition, magnetic particles entrapped
the reaction, the catalyst is dissolved in the reaction medium. in highly cross-linked imidazolium salts and an unmodified
When the reaction is complete, the solvent is removed causing silica gel were used as supports.59
re-adsorption of the catalyst, whereas the final product is Oxidation reactions of primary and secondary benzylic and
extracted by using a suitable solvent which does not dissolve aliphatic alcohols were carried out by using bis(acetoxy)iodo-
the adsorbed catalyst (Fig. 6). benzene (BAIB) in dichloromethane at room temperature
An example of this methodology was applied in the asym- (Scheme 14). Catalysts 21a,b were adsorbed in 12.5 or 25 wt%
metric aldol reaction between cyclohexanone and several benz- and used in 1 or 10 mol%. Under the adopted conditions, cata-
aldehydes. In this case, the imidazolium-tagged proline lysts 21a,b were soluble and were acting in a homogeneous
catalyst 17 was adsorbed in about 14 wt% on an imidazolium- fashion. When the reaction was complete, dichloromethane
modified silica gel support 18 to give the catalytic system 19.57 was removed under reduced pressure and the residue was
Previous studies under homogeneous conditions demon- washed with diethyl ether which removed only the carbonyl
strated the high stereoselectivity of catalyst 17.58 product, leaving catalysts 21a,b on the surface of the support.
In order to increase the affinity toward the surface of the Products were obtained in high yields and several cycles were
support, the bis-triflimide anion was used on both the support
and the catalyst. The catalytic system 19 was used in 5 mol%
by using 5 equivalents of cyclohexanone and 1.2 equiv. of
water. Under these conditions, proline 17 was soluble and is
released in solution, and is acting as a homogeneous catalyst.
When the reaction was complete, cyclohexanone/water was
removed under reduced pressure and the residue was washed
with diethyl ether which removed only the aldol product
leaving proline 17 on the surface of the support. Then, the
catalytic material was employed in the next cycle. Aldol pro-
ducts were obtained in high yields and stereoselectivities
(Scheme 13).
The role of the support was demonstrated with the follow-
ing set of experiments: (a) the use of an unsupported catalyst
gave a lower yield after 3 cycles; (b) the use of an unmodified Fig. 7 Imidazolium-modified silica 20 and catalysts 21a,b.

silica gel as a support gave a low yield (36%) and low stereo-
selectivity already in the first cycle; (c) the use of a hydrophobic
support such as a C-18 silica gel gave a drop in yield in the
second cycle. In order to demonstrate the robustness of the
support 18, catalyst 17 was washed out with methanol from a
sample used for the several cycles. Freed solid material 18 was
then reloaded with a fresh 17 in the same loading to give a Scheme 14 Oxidation of alcohols mediated by supported catalysts 21a,b.

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carried out (up to 13 cycles) without loss in activity. When an
unmodified silica gel was used as a support and the catalyst
was employed in 1 mol% a great drop in activity was observed
after 3 cycles.
By using EPR spectroscopy it was proposed that in the first
cycle the catalyst is released in solution as nitroxide species
whereas in successive cycles the catalyst is adsorbed/released
as an oxoammonium salt (Scheme 15).
Also supported metal catalysts can be released from
the support, acting as homogeneous catalysts and, finally,
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recaptured. Evidence of such behaviour was reported, for
instance, for nickel and palladium catalysts. A detailed study
was reported about Ni on charcoal.60 This catalyst was
employed in the aromatic aminations and Kumada couplings
and it was demonstrated that Ni/C was most likely of a homo-
geneous nature. The existence of an equilibrium for this
homogeneous species between nickel located inside vs.
outside the pore system of charcoal strongly favored the
former, thus leaving only traces of metal detectable in solu-
tion. After filtration a complete recovery of nickel on the char-
coal was observed allowing the recycling of the catalyst.
Palladium immobilized on several supports (carbon, silica,
and alumina) behaved similarly when employed in the
Suzuki61 or in the Heck reaction.62 However, the properties of
Pd catalysts (support, oxidation state, dispersion, and water
content) as well as experimental parameters (temperature,
solvent, base, and addition of reducing agents) were found to
be important for the re-deposition of the leached metal.
Soluble Pd species included different molecular species in
equilibrium with soluble clusters or NPs, according to the
general mechanism observed in solution.63
Supported imidazolium salts were also employed for the
release and catch of palladium-based catalysts. A detailed
study of a catalytic system in which palladium was
Scheme 15 Proposed adsorption–desorption equilibrium and
mechanism.
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immobilized onto gel-supported ionic liquid-like phases
(g-SILLPs) based on gel-type polystyrene-divinylbenzene
(PS-DVB) resins was described.64 The catalytic behaviour of the
corresponding supported Pd species was investigated for the
Heck coupling reaction between iodobenzene and methylacry-
late. Palladium was initially supported on the g-SILLPs as Pd-
NHC complexes. Such Pd-g-SILLPs materials acted as precata-
lytic species. These Pd-NHC complexes gave rise, under the
reaction conditions, to the formation of soluble Pd species,
which were responsible for the catalytic activity.9 The agglo-
meration of the soluble Pd clusters/NPs would give place to
the formation of inactive Pd black particles, but the presence
of g-SILLPs provided a different outcome, as those soluble
clusters can be recaptured and stabilized to form new sup-
ported PdNPs-g-SILLPs.
The polymer bearing ionic liquid-like units behaved as the
analogous ILs in solution stabilizing the PdNPs against the
aggregation. Indeed, when the reaction was carried out at
130 °C with high loading resin 22, no leaching was observed
(Scheme 16). Accordingly, g-SILLPs were able to scavenge
soluble palladium species from solution. The recovered cata-
lyst was reused for a further 4 cycles and, in all cases, yields
>95% for the main product, after 180 min, were achieved. Fur-
thermore, the kinetic profiles in the successive runs were very
similar.
Further studies on this topic were developed by using a
highly cross-linked imidazolium salts network covalently
immobilized on the surface of silica gel. Four different linkers
were used to connect the imidazolium moieties and palladium
was immobilized as PdCl42− followed by reduction with NaBH4
to give catalysts 23a–d (Fig. 8a).65 In a previous work, only cata-
lyst 23d was examined, and recycling studies were carried out
under batch conditions in the Suzuki reaction between 4-bro-
mobenzaldehyde and phenylboronic acid.66 Then, catalysts
23a–d were examined with a large set of substrates to give
biphenyls in high yields. Starting from the optimized batch
protocol it was investigated how to realize a flow procedure to
optimize the efficiency of isolation of the pure products and
minimize the waste associated with the process (E-factor). A
reactor scheme was set with the intention of exploiting the
reaction Scheme 16 Structure of catalyst 22 and Heck reaction between iodobenzene
and methyl acrylate.
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Fig. 8 (a) General structure of Pd-supported catalysts 23a–d; (b) schematic of
the cyclic continuous-flow reactor.
observed phenomenon related to the release and catch cataly-
tic mechanism.
The flow protocol was realized charging the base (K2CO3)
and the catalyst (23a or 23b) into two separate low-pressure
glass columns (Fig. 8b). Reactants (40 mmol of arylbromide
and 45.2 mmol of phenylboronic acid) in ethanol 96% were
charged into a third column used as a reservoir. This protocol
furnished also a unique opportunity for the minimization of
waste associated with the reaction. In fact, charging K2CO3 in
a separate column makes the recovery of Pd-catalyst very
simple and efficient since the catalyst is safely charged into
the glass column and can be directly reused for at least 4 con-
secutive runs showing an unchanged efficiency (Scheme 17).
Although the reaction was carried out using two separate
columns containing the catalytic material and the base,
respectively, a very high catalytic efficiency was observed. This
was ascribed to a release and catch mechanism in which the
supported palladium catalyst serves as a reservoir for active Pd
species that are dissolved from the solid catalyst. The active Pd
species goes through the apparatus; then, it is re-captured. As
a proof of this mechanism, ICP-OES analysis of the final
product showed the presence of only ca. 0.015 wt% of palla-
dium (referred to the initial Pd content in the catalyst).
Also linear polystyrene-stabilized PdO nanoparticles
(PS-PdONPs) were found to be an active catalyst working with
the same principle.67 Such material was prepared through the
thermal decomposition of Pd(OAc)2 in the presence of poly-
styrene. In the Suzuki coupling reaction of aryl bromides with
arylboronic acids in the presence of PS-PdONPs, no leaching
of palladium into the reaction solution occurred after the reac-
tion, as confirmed by ICP-AES analysis.68 On the other hand,
19% of palladium leached into the aqueous solution when the
Scheme 17 Recycling study on Suzuki reaction performed under release and
catch flow conditions.
2616 | Green Chem., 2013, 15, 2608–2618
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Green Chemistry
Scheme 18 Recycling study on Suzuki reaction performed using PS-PdONPs.
mixture of PS-PdONPs and bromobenzene was heated in
aqueous KOH solution at 80 °C for 1 h. To increase the stabi-
lity of the leached palladium species, a Suzuki coupling reac-
tion of chlorobenzene with 4-methylphenylboronic acid in
aqueous KOH solution was carried out in the presence of tetra-
butylammonium bromide (TBAB) as a water-soluble stabilizer.
The corresponding biphenyl was obtained in 92% yield
(Scheme 18).
The catalyst was recovered and reused up to five times with
unchanged yields from the 3rd to 5th cycle (76%). ICP-AES
analysis revealed that no palladium species remained after the
reaction and quantitative recovery of palladium was achieved.
These results suggested that the leached palladium species
participated in the catalytic process and redeposited onto
linear polystyrene after the reaction was complete.
Finally, a release and catch mechanism has been claimed
in the case of the olefin metathesis reaction catalyzed by
Grubbs–Hoveyda complexes 24 which is also termed as a
release–return mechanism69 or boomerang catalysis.70
However, the debate about the importance of such a mechanism
is open. The question is whether this mechanism contributes
substantially,71 in part69 or does not contribute.72 A proposed
route for the release and catch mechanism is described in
Scheme 19. The initiation step (release) involves dissociation
of the benzylidene ether. After initiating several catalytic olefin
metathesis cycles ( propagation), the bidentate isopropoxy
styrene returns to the ruthenium as a benzylidene ligand
(catch). Evidence of this mechanism has been found working
at high catalyst loadings (5–10 mol%). Based on this
Scheme 19 Proposed route for the release and catch mechanism of Ru com-
plexes 24.
This journal is © The Royal Society of Chemistry 2013

Green Chemistry
mechanism, it could be possible to recover and reuse the cata-
lyst by using a supported variant (i.e., sol–gel supported-,69
CNTs-supported-45 or ionic liquid-tagged Ru-based
complexes).73–75
On the other hand, investigations based on fluorescence
spectroscopy on a fluorophore-tagged Grubbs–Hoveyda
complex, UV-Vis experiments and 19F NMR spectroscopy on a
fluorine-substituted complex did not provide evidence that the
release and catch mechanism was operative.72 Such experi-
ments were carried out using low catalytic loading ( just
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sufficient to effect the reaction). It has been suggested that the
re-isolation of the Grubbs–Hoveyda complex following olefin
metathesis reactions is primarily caused by incomplete acti-
vation of the initial Grubbs–Hoveyda complex. If the olefin
metathesis reaction is faster than the release step or if much
more catalyst is used than is required, then an incomplete
release of the initial complex occurs. When low catalyst load-
ings are used, most of the complex will undergo activation
(release).
Conclusions
The reported studies confirm the interest of the scientific com-
munity in the development of a new strategy for catalyst re-
cycling. Such a strategy is based on: (a) selective
immobilization of the catalyst on tailor-made supports (i.e.,
carbon nanotubes, silica, alumina, and supported ionic
liquids) via different kinds of molecular recognition (i.e., π–π
stacking, hydrogen bonding) or via nanoparticles stabilization,
(b) the subsequent release of the catalyst during the reaction
and (c) the recapture of the catalyst at the end of the reaction.
Such a “catalyst-sponge like” system allows one to combine
the benefits of homogeneous and heterogeneous catalysis and
can be applied to expensive organometallic-based catalysts,
organocatalysts and metal-based catalysts both for batchwise
reactions and flow reactions.
However, the present approach deserves more in-depth
investigations since it is still in its infancy and, in several
cases, further optimizations are required, especially from the
green chemistry viewpoint. Indeed, often the solvents used are
not the best environmentally-friendly ones, chromatographic
purification is needed and, in many cases, loss in activity or
leaching is observed upon recycling. However, encouraging
results have been reported from a green chemistry standpoint
such as the hydroxycarbonylation of aryl halides (Scheme 4) or
the Suzuki reaction under flow conditions (Fig. 8).
Nevertheless, the concept is interesting and further useful
applications are expected in the near future.
Acknowledgements
Financial support from the University of Palermo (funds for
selected topics) is gratefully acknowledged.
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Perspective
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