Challenges in The Catalytic Synthesis of Cyclic and Polymeric Carbonates

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Cite this: Catal. Sci. Technol., 2012, 2, 21692187
PERSPECTIVE
www.rsc.org/catalysis
Challenges in the catalytic synthesis of cyclic and polymeric carbonates

from epoxides and CO2
Paolo P. Pescarmona* and Masoumeh Taherimehr
Published on 29 June 2012. Downloaded on 18/02/2015 14:06:27.
Received 30th May 2012, Accepted 26th June 2012

DOI: 10.1039/c2cy20365k
The addition of carbon dioxide to epoxides to produce either cyclic carbonates or polycarbonates
is an important reaction allowing the conversion of a renewable, inexpensive and non-toxic
feedstock such as CO2 into useful products with many potential applications. In this perspective
article, an overview of the type of catalysts used for this reaction, the mechanisms with which
they operate and the parameters inuencing their activity and selectivity are presented and
discussed critically. In this context, the main challenges to be tackled in this vibrant area of
research are highlighted.
1. Introduction
The growing concerns about the environmental impact of
carbon dioxide emissions produced by fuel combustion and
other human activities prompted the scientic community to
research ways to store or, preferably, reuse this molecule.1
In this context, the chemical xation of CO2 to produce useful
compounds has attracted increasing interest.2,3 Carbon dioxide is
an inexpensive, widely available, non-toxic and renewable carbon
Centre for Surface Chemistry and Catalysis, KU Leuven, Kasteelpark

Arenberg 23, 3001 Heverlee, Belgium.
E-mail: paolo.pescarmona@biw.kuleuven.be
Paolo Pescarmona was born in

1973 in Torino, Italy. After
receiving his Master Degree
in Chemistry from the University of Torino, he moved to the
Netherlands where he obtained
his Ph.D. from the Delft
University of Technology in
2003. Since 2005 he works at
the University of Leuven (KU
Leuven), Belgium, rst as
post-doc researcher and since
2008 as professor. Presently,
his group consists of six Ph.D.
Paolo P. Pescarmona
students and two post-doc
researchers. His research
interests are steadily growing and embrace many aspects of
catalysis and of materials chemistry. A common thread in his
research is the attention towards sustainability, as exemplied
by the topic of this perspective article. His curiosity is not limited
to chemistry and he is keen on travelling and learning about
dierent cultures around the world.
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The Royal Society of Chemistry 2012
source, but its use as feedstock for the production of valuable

chemicals faces the challenge of its high thermodynamic stability.4
This implies that the conversion of carbon dioxide may require
a high energy input, as in the case of the photocatalytic
reaction with water to generate oxygen and methanol or
methane.5 An alternative approach consists in the reaction
of CO2 with compounds with a relatively high free energy, thus
providing a thermodynamically favourable process.4 Among
the reactions employing this last strategy, the addition of
carbon dioxide to epoxides is a relevant topic of research since
it is an atom-ecient reaction that can generate useful classes
of compounds as cyclic carbonates and polycarbonates
(Scheme 1).4,69 This perspective article focuses on this reaction
Masoumeh Taherimehr
Masoumeh Taherimehr was

born in 1983 in Ahvaz, Iran.
In 2005 she received the
Degree in Chemistry from the
Chamran University of Ahvaz
and in 2007 she obtained
her Master Degree from the
Lorestan University, Iran. In
2010 she started her Ph.D. at
the KU Leuven under the supervision of Prof. Pescarmona.
Her research interests include
homogeneous and heterogeneous catalysis for the
synthesis of organic compounds
from renewable sources, with a
focus on the conversion of
carbon dioxide to valuable
products.
Catal. Sci. Technol., 2012, 2, 21692187
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Scheme 1 Possible products of the reaction of CO2 with epoxides: cyclic carbonate (a), polycarbonate (b) and polycarbonate containing ether
linkages (c).
and on the catalytic systems used to promote it, with the

purpose of providing a systematic analysis of the topic and of
underlining the challenges that still need to be tackled. Both
cyclic carbonates and polycarbonates are valuable compounds with
many established and potential applications. Cyclic carbonates are
the thermodynamically favoured products of the reaction of
epoxides with carbon dioxide.4,6,8 Their application range
is broad, the most employed compounds being ethylene
carbonate and propylene carbonate.4,6,7 Cyclic carbonates
can be used as intermediates in the synthesis of ne or bulk
chemicals,1,6 as exemplied by the Asahi Kasei industrial
process for the production of polycarbonates from bisphenol
A.10 This multi-step process involves the use of ethylene
carbonate as reagent and represents a greener alternative to
the currently main industrial process, which is based on the
highly toxic phosgene as reagent. Other applications of cyclic
carbonates are as environmentally friendly polar aprotic
solvents, with low odour and toxicity,7,11,12 and as electrolyte
solvents for lithium-ion batteries.13 The second class of
organic carbonates that can be obtained by the reaction of
carbon dioxide with epoxides are the polycarbonates. At this
stage, it is important to note that the term polycarbonate is
used to refer to various types of polymers, which can present
rather dierent physicochemical properties from each other. A
polycarbonate is dened as a polymer containing carbonate
groups (O(CQO)O) in its backbone chain: this description includes both the commercial polycarbonates that are
synthesised using bisphenol A as building block, and the
polymers obtained by the alternating copolymerisation of
CO2 with an epoxide, which are discussed in this article. The
bisphenol-based polycarbonates are thermoplastic polymers
with excellent mechanical and physical properties, including
high strength, rigidity, toughness, durability, transparency to
light, heat resistance and good electrical insulation. Owing to these
properties, bisphenol-based polycarbonates can substitute glass or
metal in many uses and nd widespread application as materials
for data storage (e.g. CDs and DVDs), for electronic components,
for lenses, as construction materials and as automotive and
aircraft components.6,10 On the other hand, polycarbonates
obtained by copolymerising carbon dioxide and epoxides
display less suitable properties including low rigidity (glass
transition temperature of 3540 1C for poly(propylene
carbonate) compared to about 150 1C for bisphenol-based
polycarbonates) and moderate thermal stability.8,14 So far
these features limited the application of these polymers,14
despite their biodegradability and the fact that they can be
prepared in a green process from renewable carbon dioxide.
These observations lead us to the identication of a rst
challenge (1): the properties of alternating copolymers
obtained from the coupling reaction of carbon dioxide and
2170
epoxide should be improved in order to attain practical applications for these materials. This might be achieved by investigating
dierent types of epoxides as substrates for the copolymerisation
reaction with CO2; by optimising the catalysts in order to
increase the molecular weight and crystallinity of the polymers;
by cross-linking the polymer chains; by copolymerisation
involving two dierent epoxides or an epoxide and another
type of monomer; through the use of llers during the synthesis to
form (nano)composites; through blending with other polymers.14,15
The improved polymeric materials could nd a vast range of
applications as engineering thermoplastics, elastomers, packaging
materials, binders, adhesives and coatings.8,14
From the point of view of green chemistry and sustainability,
the relevance of the synthesis of organic carbonates through the
reaction of carbon dioxide with epoxides lies in the low cost,
availability and renewable character of CO2 as carbon source
and in the features and potential applications of the products:
cyclic carbonates can be used as green solvents and provide
an alternative to the use of the highly toxic phosgene as
reagent,7,10,11 while polycarbonates could substitute synthetic
polymers prepared from non-renewable petroleum feedstock.8
On the other hand, it should be noted that the benets on the
mitigation of the impact of CO2 emissions through this reaction are expected to be limited.16 Presently, only B0.5% of the
CO2 generated by human activities is reused by the industry,
and of this amount only a small fraction is employed for the
synthesis of organic carbonates (i.e. acyclic carbonates, cyclic
carbonates and polycarbonates).1 The processes for the synthesis
of organic carbonates have the potential to reach a larger scale,
particularly if the applicability of the products and the eciency
of their synthesis will be improved (see next sections for a more
detailed discussion). However, the yearly need for these and
other compounds that could be produced by CO2 xation is
likely to remain low compared to the yearly amount of CO2
generated worldwide by fuel combustion. The minimisation
of carbon dioxide emissions will require most probably a
combination of approaches including the use of greener energy
sources as alternative to fossil fuels,1 the improvement of the
eciency of existing processes generating CO2 as a waste
(e.g. transportation, heating, industrial processes) and worldwide
policies to avoid an unsustainable growth of the human population.
In this perspective article, the dierent mechanisms leading
to the catalytic synthesis of either cyclic or polycarbonates
from the reaction of carbon dioxide with epoxides are reviewed
and rationalised, and the parameters governing the activity and
the selectivity of the catalysts are critically discussed. The denition
of this general picture provides the context to introduce the various
open challenges in this eld of research. The target of this article is
to help understanding the catalytic systems used for this reaction
and to suggest relevant research directions, and not to provide
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Scheme 2 Possible intermediates of the reaction of epoxides with CO2, exemplied in the case of the reaction catalysed by a metal complex. Nu is
a nucleophile that can originate from the metal complex or from a co-catalyst. RO- is an alkoxide or an aryloxide that can act as a nucleophile. The
dotted arrows indicate the possible back-biting reactions that would lead to the formation of cyclic carbonate.
a comprehensive overview of all homogeneous and heterogeneous

catalysts reported for the reaction of CO2 with epoxides, for which
purpose excellent reviews are available.4,69,14,1719
2. Mechanism of the addition of carbon dioxide to

epoxides
The reaction of CO2 with epoxides can generate two types of
products: cyclic carbonates and polycarbonates (a and b in
Scheme 1). Moreover, the consecutive insertion of two epoxides
in the polymer chain can occur instead of the alternating
copolymerisation of carbon dioxide and epoxide.8,14 This leads
to the presence of ether linkages in the polycarbonate (c in
Scheme 1), or to the formation of polyethers in the extreme
case of polymerisation occurring exclusively between epoxide
molecules (m = 0 in structure c).
The addition of CO2 to epoxides is generally carried out in
the presence of a catalytic system that can initiate the reaction
by activating either the epoxide or carbon dioxide, or both at
Fig. 1
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the same time. The epoxide is typically activated by interaction of

the oxygen atom with a Lewis acid, followed by a nucleophilic
attack that causes the opening of the epoxide ring. CO2 is a
linear, apolar molecule, though the two CQO bonds are polar,
implying that the carbon atom has a partial positive charge and
the oxygen atoms have a partial negative charge. Therefore, the
carbon atom can act as an electrophile and the oxygen atoms as
nucleophiles: the activation of CO2 can thus occur both through
a nucleophilic and an electrophilic attack (vide infra). It follows
from these considerations that most catalytic systems that have
been investigated for this reaction contain Lewis acid sites for the
electrophilic activation of epoxide and/or carbon dioxide and
Lewis base sites acting as nucleophiles. The two sites can belong
to two dierent compounds for example the metal of a complex
as Lewis acid and the anion of a salt as Lewis base or be parts
of a single compound, as in a complex containing a cationic
metal centre and a labile anionic ligand.
Dierent mechanisms for the reaction of carbon dioxide with
epoxides have been proposed, and in many cases demonstrated
Phenolate metal complexes.
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Fig. 2 Metal complexes with salen and related ligands.
by means of characterisation with various spectroscopic and

analytical techniques. The predominance of a specic reaction
path depends on the nature of the catalytic system, but also on
the substrate and on the reaction conditions. In all cases the
activation of the epoxide requires a nucleophile, which is
the common feature of all catalytic systems employed for the
reaction of carbon dioxide with epoxides. Regardless of the
nature of the rst step, all mechanisms involve an intermediate
containing a carbonate precursor, which can either react
further through consecutive additions of other epoxide and
CO2 molecules (propagation) to generate a polycarbonate, or
undergo a back-biting reaction leading to ring closure with
formation of the cyclic carbonate (Scheme 2). If polycarbonates are the products of the reaction, the nucleophilic species
that serves as the initiating group will also be the end group of
the polymer chain.
The most widely studied type of catalysts for the reaction

of carbon dioxide with epoxides are homogeneous metal
complexes, which can be employed alone if they contain a
ligand that can act as a nucleophile, or in combination with a
co-catalyst providing the nucleophilic species. A variety of
metal centres acting as Lewis acid sites has been studied for
these complexes: Al, Cr, Mn, Co, Fe, Cu, Zn, Cd, Mg, Li and
lanthanoids.8,14 Both monometallic and bimetallic complexes
have been employed as catalysts for this reaction. The most
common ligands used for the synthesis of these complexes are:
salen and related ligands, b-diiminates (BDI), phenolates and
porphyrins (Fig. 1, 2, 4 and 7).19 Non-metallic homogeneous
catalysts based on salts of organic cations have been reported
as well (see Section 2.3). Heterogeneous catalysts are also
known: the most widely applied is zinc glutarate, but heterogeneous systems based on the immobilisation of homogeneous
Scheme 3 Reaction of CO2 with epoxides: monometallic pathway involving one nucleophile. The nucleophile (Nu) may originate from the metal
complex or from a co-catalyst.
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Scheme 4 Reaction of CO2 with epoxides: monometallic pathway involving two nucleophiles. Note that Nua and Nub may be the same or
dierent type of nucleophile.
catalysts on a support are receiving increasing attention (see

Section 4).14,18,19
Most of the mechanisms proposed for the reaction of CO2
with epoxides have been derived from studies of homogeneous
catalytic systems, but heterogeneous catalysts are considered
to follow similar pathways.20 In order to facilitate the systematic
discussion of the various reaction mechanisms, we divided them
into three categories based on the number of metal atoms
involved in the catalytic cycle: monometallic pathways, bimetallic
pathways and non-metallic pathways.
2.1
Monometallic pathways
This type of mechanisms is exemplied by the wide group of

homogeneous catalytic systems based on metal complexes.
These metal complexes can include a ligand that can act as
nucleophile. Alternatively the metal complex, usually referred
to as the catalyst, is used in combination with an added
nucleophile generally denoted as the co-catalyst.
(a) A common monometallic mechanism for the addition of
CO2 to epoxide catalysed by a metal complex proceeds
through the steps summarised in Scheme 3. First, the epoxide
coordinates to a Lewis acidic metal centre and gets activated
towards attack by a nucleophile. The nucleophilic attack leads
to opening of the epoxide ring and formation of a metal-bound
alkoxide. This alkoxide can in turn act as a nucleophile leading to
CO2 insertion into the metal alkoxide bond, generating a metal
carbonate intermediate. This carbonate species can either evolve
towards the cyclic carbonate or propagate by further addition of
epoxide and CO2 with formation of a polycarbonate (vide supra).
The occurrence of this mechanism has been supported by an

isotope-labelling experiment.21
(b) A monometallic mechanism involving two nucleophiles
has been proposed for metal salen complexes (e.g. Cr-salen),
which are characterised by a planar conguration with a
tetradentate coordination of the salen ligand (Fig. 2). The
axial positions of the metal are available for coordination with
nucleophiles. Of the two nucleophiles involved in the mechanism,
one is part of the metal complex as axial ligand (Nua) and the
second one (Nub) is added to the system and coordinates to
the metal in the remaining trans axial position, thus generating a
six-coordinated intermediate (II in Scheme 4).9,14,22 The coordination of the second nucleophile serves to labilise the other
metal-nucleophile bond, favouring coordination and nucleophilic
attack of the epoxide (III). The formed alkoxide species (IV) acts
in turn as a nucleophile that attacks CO2 to form a metal
carbonate species. The presence of a nucleophile in the trans
position to this carbonate (V) has been reported to favour the
further nucleophilic attack and ring opening of a new epoxide
molecule (similarly to what occurs in step III). Therefore, the
alternating copolymerisation of epoxide and carbon dioxide
leading to the formation of polycarbonates is the preferential
path with this mechanism.23 In general, the nucleophiles can
be neutral or ionic species. Kinetic studies indicated that anionic
six-coordinated intermediates (II in Scheme 4) are more eective
both in the opening of the epoxide ring and in the CO2 insertion
compared to their neutral six-coordinated analogues.9 It is has
been proposed, though not unequivocally established, that both
Nua and Nub can serve as initiator groups leading to the growth
of two polymer chains from one metal centre.9,14,24
Scheme 5 Reaction of CO2 with epoxides: bimetallic pathway involving two monometallic complexes.
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Scheme 6 Reaction of CO2 with epoxides: bimetallic pathway with simultaneous activation of epoxide and CO2 on a complex with two adjacent
metal centres.
Scheme 7 Reaction of CO2 with epoxides: bimetallic pathway with complexes containing two adjacent metal centres and OR groups.
2.2
Bimetallic pathways
The addition of CO2 to epoxides can follow a bimetallic

mechanism if the catalyst contains two metal centres or if
two monometallic catalysts act in collaboration.
(a) A bimetallic pathway involving two separate metal
complexes has been inspired by a mechanism proposed for
the asymmetric ring opening of epoxides.25 This intermolecular mechanism is similar to the monometallic pathway (2.1.a),
with the dierence that the nucleophile that attacks the
epoxide activated by the metal centre is coordinated to a
second metal centre (Scheme 5).8 The bimetallic initiation is
followed by a monometallic pathway leading to cyclisation
and formation of cyclic carbonate or to propagation of the
alternating polycarbonate. Kinetic studies by means of in situ
infrared spectroscopy supported this mechanism for a Cr-salen
complex.26 This pathway is expected to occur when low
epoxide/catalyst ratios are employed.19 It has been suggested
that this mechanism tends to be followed when a weaker Lewis
base is used as co-catalyst, while mechanism 2.1.b is more
likely to occur in the presence of a stronger Lewis base that is
able to weaken the metal-nucleophile bond and allow concerted opening of the epoxide ring.27 If this mechanism is
followed, the reaction rate has a second-order dependence on
the metal concentration, while a rst-order dependence is
observed in the case of a monometallic pathway.
(b) Metal complexes containing two neighbouring metal
centres may activate epoxide and CO2 simultaneously
(Scheme 6). This promotes the intramolecular nucleophilic
attack of the alkoxide to the carbon atom of the activated
CO2 molecule. This mechanism has been proposed to explain
the improved catalytic activity of bimetallic [Al(salen)]2O
complexes (Fig. 8) compared to monometallic salen complexes.28
2174
It has been suggested that in this mechanism the co-catalyst,

tetratbuylammonium bromide (Bu4NBr), plays a second role
besides the ring opening of the epoxide by the bromide. Tetrabuylammonium bromide can decompose to tributylamine, which
can form a carbamate salt with CO2 (Bu3N+CO2) and this salt
can coordinate more easily to the second Al-centre compared to
CO2 alone.29
(c) The rst step of the catalytic addition of carbon dioxide
to epoxides is not always the activation of the epoxide. Some
metal complexes containing an alkoxide or aryloxide group
(OR) are able to undergo CO2 insertion to form a bidentate
carbonate as the rst step (Scheme 7).8,14 This is not unexpected,
because the OR groups are analogous to the alkoxide intermediates formed upon epoxide insertion in the monometallic
mechanisms described above, and such metal-bound alkoxides
are able to react with CO2 (see Section 2.1). The reaction
continues through the coordination of the epoxide followed by
ring opening and insertion into the metal carbonate bond, which
was proposed to be the rate-determining step of the process.30
This type of mechanism has been proposed and investigated in
detail for bulky b-diiminate zinc complexes containing two
adjacent metal centres bridged by alkoxide (or carboxylate)
groups (Fig. 4).8,30 b-Diiminate zinc complexes can exist both
in dimeric (bimetallic) or monomeric (monometallic) form. The
most likely pathway is bimetallic, as sketched in Scheme 7, but
a contribution from a monometallic mechanism cannot be
excluded.30 The prevalence of the monomeric or dimeric form
of the complex in solution strongly depends on the steric
hindrance of the substituents.8 Catalysts for which the rst
step of the mechanism is CO2 insertion with formation of a
bidentate species generally display high selectivity towards the
copolymerisation reaction.8,9 In this context, it has been
suggested that the presence of two adjacent metal centres
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Scheme 8
Reaction of CO2 with epoxides: non-metallic pathways with epoxide activation as the rst step (a) or with CO2 activation as the rst step (b).
can promote the selectivity of the reaction towards the growth

of a polycarbonate chain by simultaneously coordinating two
species (see Scheme 7), thus favouring the interaction of the
growing chain with new incoming reagents.19 Nevertheless, the
presence of two neighbouring metal centres is not a sucient
condition for selectively generating polycarbonates, as proven
by the high selectivity towards cyclic carbonate displayed by
Al-salen bimetallic complexes following mechanism 2.2.b.28
2.3
Non-metallic pathways
Salts of organic cations have been employed alone as catalysts

for the reaction of carbon dioxide with epoxides. Particularly,
ionic liquids have been studied either as homogeneous or
heterogeneous catalysts, in the latter case in the form of
supported species.18 Carbon dioxide can dissolve in considerable amounts in ionic liquids, implying that the ionic liquids
can be employed with the double role of solvents and catalysts.
In general, reactions with ionic liquids as catalysts without the
assistance of metal centres require relatively high temperature
( Z 80 1C) in order to achieve good product yields, thus
favouring the formation of the thermodynamically more
stable cyclic carbonate as the main product. The mechanism

followed by these non-metallic catalysts depends on the nature
of the anion and cation (X Y+) constituting the salt. Two
possible pathways may lead to formation of the carbonate
product (Scheme 8):
(a) The most common mechanism involves a nucleophilic
attack of the epoxide by the anion, which causes opening of
the epoxide ring, followed by the insertion of carbon dioxide
and nally by ring closure to generate the cyclic carbonate.
This mechanism is very similar to the monometallic pathway
described in 2.1.a.
(b) If the anion is bulky (e.g. BF4, PF6), the interaction
between the epoxide and the anion is very weak and the anion
rather interacts with CO2 to generate a new ionic species
[XCO2], that is more basic than the original anion X
and thus able to attack the epoxide to generate a carbonate
intermediate and nally the cyclic product.18 This pathway
was proposed on the basis of a mechanistic study by means of
in situ ATR infrared spectroscopy.31
The heterogenisation of ionic liquids has been employed as a
strategy to develop recyclable catalysts for the synthesis of
cyclic carbonate from CO2 and epoxide.3236 Among these
Scheme 9 Synthesis of cyclic carbonate catalysed by an immobilised ionic liquid with a side chain terminating with an OH group.
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supported ionic liquids, the imidazolium-based ionic liquids

containing an OH or a COOH group in the cation are
particularly interesting from a mechanistic point of view.34,35
It has been proposed that the OH of the alcoholic or carboxylic
group can interact with the oxygen atom of the epoxide, thus
helping the nucleophilic attack of the epoxide by the anion
(Scheme 9). The role of the OH is similar to that of the Lewis
acidic metal centre in the metallic mechanisms (vide supra).
3. Catalytic activity and selectivity in the synthesis

of cyclic carbonates and polycarbonates
As discussed in Section 1, cyclic carbonates and polycarbonates
are both relevant compounds. However, if we want to design a
catalyst that is able to produce any of them eciently it is
crucial to understand and control the parameters determining
the selectivity of the reaction of CO2 and epoxides towards each
of these two families of carbonates (challenge 2). The formation
of polycarbonates is thermodynamically less favourable than
the synthesis of cyclic carbonates, but it generally requires lower
activation energy.9,37 This means that by selecting a suitable
catalytic system and by tuning the reaction conditions it should
be possible to selectively produce either one or the other type of
carbonate. In the case in which the polycarbonate is the desired
product it is also important to avoid the formation of polyether
linkages (see Section 2) and to achieve polymers with high
molecular weight and low polydispersity. These parameters can
play a relevant role in obtaining polycarbonates with suitable
properties for application (see challenge 1). The control of the
selectivity is not the only challenge connected to the design of
improved catalysts for this reaction. The catalytic activity can
still be improved compared to the already known, promising
catalysts, in order to reach higher turnover frequencies under
mild temperature and pressure conditions with dierent types of
substrates, including sterically hindered and internal epoxides
and oxetanes (challenge 3).
A rationalisation of the factors determining the activity and

selectivity of known catalysts for the reaction of CO2 with
epoxides can be very useful for designing novel catalysts with
improved performance. For this purpose, the inuence of the
nature of the catalyst, of the co-catalyst (if present), of the
substrate and the role of the solvent and of the reaction
conditions will be analysed and discussed in this section for
selected catalysts reported in the literature.
3.1 Metal-containing catalysts
Metal complexes are the most widely studied class of metalcontaining catalysts for the reaction of carbon dioxide with
epoxides (see Section 2). The knowledge gained by studying the
parameters that inuence the catalytic behaviour of these complexes
can be rather general and apply to other catalytic systems, including
heterogeneous ones. Both the metal and the ligands play a role
in dening the properties of metal complexes as homogeneous
catalysts for the reaction between CO2 and epoxides.
(a) The nature of the metal centre in metal complexes plays a
crucial role in their catalytic performance. The monometallic and
bimetallic pathways discussed in Section 2 are characterised by
alkoxide and carbonate intermediates containing a metaloxygen
bond. The strength of this bond is an important factor in
determining the activity and selectivity of the catalyst. A too
strong metaloxygen bond makes the intermediate inactive
both towards another insertion, which would lead to propagation and copolymer production, and towards ring closure,
which would yield a cyclic carbonate. On the other hand, a
weak metaloxygen bond can be displaced by a nucleophile or
a solvent molecule, leading to lower activity but also favouring
the back-biting reaction and, thus, increasing the selectivity
towards the cyclic carbonate. It can be concluded that intermediate bond strength is needed for a good catalytic performance and that the properties of the catalyst can be tuned by
the choice of the metal centre.38 The relevance of the nature of
the metal centre can be recognised by comparing the catalytic
Selected metal complexes as catalysts for the reaction of CO2 with epoxides
Table 1
Catalyst
PDId
Catalyst
T/ p(CO2)/ Reaction
TOFc/ Major carbonate product Mn
(kg mol1) (Mw/Mn) Ref.
Epoxidea loading/mol% 1C bar
time/h
TONb h1
[selectivity (%)]
1a
1b
2a
2b
3a [X = F, L = THF]
4b/PPNCl
5b [X = OCCCl3]/PPNCl
5c/PPNCl
6b/Bu4NI
7a [X = NO3]/DMAP
8/PPNCl
9
10
11 [R = iPr, R 0 = Me]
13d
14c
15b/DMAP
16/Bu4NBr
CHO
CHO
CHO
CHO
CHO
PO
PO
PO
SO
PO
CHO
PO
PO
CHO
CHO
CHO
CHO
SO
5
0.67
0.1
0.1
0.1
0.05
0.05
0.05
2.5
0.1
0.1
0.05
0.001
0.1e
0.1
0.009
0.2
2.5
60
60
80
80
80
25
25
25
45
25
70
25
70
50
50
80
80
25
1
1
1
1
55
15
15
1.5
10
15
34
14
20
7
7
12
50
1
6
2
24
2
48
2
1.5
2
3
3
2
12
1
2
0.5
10
24
3
10
43
219
170
364
39
1540
16 000
449
364
2720
500
12
2
22
9
86
8
328
568
235
13
86
230
128
16 000
224
729
272
21
4
Polycarbonate
Polycarbonate
Polycarbonate [96]
Polycarbonate [499]
Polycarbonate
Polycarbonate [499]
Polycarbonate [499]
Polycarbonate [499]
Cyclic carbonate [499]
Polycarbonate [499]
Polycarbonate [499]
Polycarbonate [99]
Polycarbonate [499]
Polycarbonate [95]
Polycarbonate
Polycarbonate
Polycarbonate [499]
Cyclic carbonate [499]
19.2
12.6
6.2
5.1
42
25.4
28.1
15.5
13.2
91
23.9
300
19.1
23.3
261
14.5
1.56
1.29
1.19
1.26
6
1.14
1.14
1.18
1.29
1.15
1.14
1.31
1.07
1.15
1.6
1.13
39
37
42
43
56
45
45
45
69
22
50
51
54
59
30
61
67
68
a
CHO = cyclohexene oxide; PO = propylene oxide; SO = styrene oxide; b TON = mol of epoxide converted per mol of metal; c TOF = mol of
epoxide converted per mol of metal per hour; d PDI = polydispersity index; Mn = number average molar mass; Mw = weight average molar
mass; e Based on the monomeric complex.
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behaviour of complexes with the same ligand scaold but with

dierent metal centres.
Replacing the two zinc atoms in the bimetallic phenolate
complex 1 in Fig. 1 with magnesium atoms increased the
catalytic activity if the reaction was carried out at low CO2
pressure (1 atm, see Table 1).14,37,39 It was hypothesised that the
harder Lewis acid nature and higher oxophilicity of Mg2+ in
comparison with Zn2+ might make the former more eective
for epoxides activation under these reaction conditions.37
Compared with their organozinc counterparts, many
organoaluminium-based catalysts are less active and selective
in the synthesis of polycarbonates and tend to promote cyclic
carbonate production.40 An explanation for the preferential
formation of cyclic carbonates with aluminium salen complexes
has been provided by theoretical calculations.41 It was found
that the dissociation of the growing polymer chain from
aluminium salen complexes is more favourable than from
chromium salen complexes. The dissociation can be followed
by ring closure with formation of the cyclic carbonate, thus
accounting for the higher selectivity towards this product.
Dizinc macrocyclic complex 2a in Fig. 1 displays high
activity in the copolymerisation of CO2 and cyclohexene oxide
at low CO2 pressures.42 This catalytic behaviour was attributed to
the coordinative exibility of the ligand and to the vicinity of
the two metal centres, which can facilitate bidentate binding of the
growing carbonate chain (see mechanism 2.2.c), thus lowering the
activation energy for CO2 insertion.14 Replacing zinc with cobalt
(2b) in this type of bimetallic complexes caused a signicant
increase of the catalytic activity (Table 1). Considering that the
rate determining step is likely to be the epoxide ring opening by the
nucleophilic carbonate chain, the higher activity of the cobalt
complex can be attributed to an increased nucleophilicity of the
carbonate propagating species in the attack of the epoxide ring
when the metal centre is Co(II) compared to Zn(II).43
The electronic conguration of the metal centre can
determine the type of coordination of the metal complex. In
the case of metal salen catalysts (Fig. 2), it has been shown that
a six-coordinated metal complex with a distorted octahedral
geometry (see mechanism 2.1.b) is necessary for the alternating
copolymerisation to proceed eciently.44 For example, sixcoordinated salen complexes with high catalytic activity are
formed with chromium(III) and cobalt(III), which have half-lled
t2g orbitals. On the other hand, Schi base Mn(III) complexes
are preferentially ve-coordinated. These Mn-complexes have
low tendency to bind the epoxide substrates and, therefore, are
ineective in catalysing the reaction between CO2 and epoxides.
(b) The ligands in a metal complex can be strongly coordinated to
the metal centre or be labile. Both types play a role in determining
the electronic and steric properties of the metal complex. The latter
ones can also actively participate in the catalytic reaction. From
these considerations, it becomes clear that a careful selection of the
ligands is crucial for optimising the catalytic activity and selectivity
of metal complexes.
The importance of the strength of the metaloxygen bond in
the alkoxide and carbonate intermediates was underlined in
Section 3.1.a. The strength of this bond is not only inuenced
by the metal, but also by the nature of the ligand(s) coordinated
to it. Electron-donating ligands and electron-donating groups
on the ligands can lead to a decrease in the metaloxygen bond
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strength, thus favouring the back-biting reaction and increasing the

selectively towards the production of cyclic carbonate. Conversely,
electron-withdrawing groups will decrease the electron density
of the metal centre, thus increasing its Lewis acid character.
The role of the ligand is intimately related to that of the metal
centre, of the co-catalyst and of the reaction conditions.
Therefore, the optimum features of the ligand can be extremely
dierent for dierent systems. Many studies demonstrated the
impact of changes in the structural and chemical features of the
ligand and in the nature of its substituents on the catalytic
activity and selectivity of metal complexes.
Various studies on the eect of changes in the structure
and in the substituents of the ligand have been carried out with
metal salen complexes. In the case of cobalt salen complexes
(X = OOCCCl3, complexes 4a, 4b and 5b in Fig. 2), ligands with a
non-cyclic diimine backbone showed lower catalytic activity for
copolymerisation of propylene oxide and CO2 compared to their
counterparts with the cyclic diimine backbone (Table 1). Moreover,
it was found that electron-withdrawing substituents in the paraposition of the phenolate are detrimental to the copolymerisation
activity (compare 5b with X = OOCCCl3 and 5c in Table 1).45
The substituents on the aromatic ring of the salen ligand
can also have a steric eect: in the reaction of styrene oxide
with CO2, a signicant decrease in the activity and polymer
selectivity of a Co-salen complex was observed when changing
the groups in the ortho-position of the phenolate from tert-butyl
to very bulky groups (i.e. CMe2Ph, SiMe2tBu, see 5b with
X = DNP and 5d in Fig. 2).46
Changing the cyclohexane moiety of the diimine backbone of a salen ligand to a phenyl group (salphen ligand, 6 in
Fig. 2) was reported to aect the selectivity of the chromium
complex in the reaction of CO2 with propylene oxide. The
Cr-salphen complex (6a) has a fully conjugated ligand structure and
is more selective towards poly(propylene carbonate) (if using no
more than one equivalent of co-catalyst, see Section 3.2.a). The
Cr-salen complex (5a with X = Cl) has a non-conjugated fragment
and is more selective towards cyclic propylene carbonate. This
result was explained by the more electron-donating nature of
the salen ligand, which weakens the metaloxygen bond, thus
favouring the dissociation of the intermediate species and leading
to the cyclic product (see Section 3.1.a).47
The complexity of the catalytic reaction of carbon dioxide
and epoxides is underlined by the dierent eects that a same
change in the ligand can have with dierent metals. Switching
from a salen to a salphen ligand had a major eect on the
catalytic activity of Zn complexes employed with Bu4NI as cocatalyst but did not aect the selectivity, which was directed
towards cyclic carbonates with a variety of epoxides (5e and 6b
in Fig. 2 and Table 1).48 The higher activity of the Zn-salphen
complexes stems from the higher Lewis acidity of the zinc
centre, which is ascribed not only to the electronic eects of
the ligand but also to the rigid, planar geometry imposed by
the ligand scaold. The eect of the substituent in the paraposition on the phenolate was also investigated (6b and 6c in
Fig. 2): bulky groups in these positions are needed to prevent
the dimerisation of the Zn-salphen complexes, which would
cause a dramatic drop in catalytic activity.49
The nature of the ligand determines whether the complex
has a rigid or exible structure. In dierent contexts, both
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Fig. 3 Cobalt salen complexes with functionalised side arms.
features have been claimed to be advantageous. Chromium salan

complexes (7 in Fig. 2 and Table 1) contain nitrogen atoms with
sp3 hybridisation, which makes them more exible than salen
complexes and decreases the electrophilicity of the metal centre.
These features were proposed to favour the dissociation and
re-association of the co-catalyst and of the growing polymer
chain, thus explaining the much higher activity in the reaction of
propylene oxide and CO2 with the salan complexes compared to
their salen counterparts (7a and 7b vs. 4c and 4d).22 Similarly, the
high activity of the chromium salalen complex 8 (where the
salalen ligand contains a nitrogen atom with sp2 hybridisation
and the other with sp3 hybridisation, see Fig. 2 and Table 1) in
the copolymerisation of cyclohexene oxide and CO2 under mild
conditions was ascribed to its coordinative exibility, which can
allow bidentate binding of the growing polymer chain, thereby
decreasing the energy barrier for CO2 insertion.50 More in
general, it has been suggested that the ability of a metal complex
to aord bidentate coordination or coordination of two species
(i.e. epoxide and carbonate or CO2 and ring-opened epoxide) at
the same time, tends to favour the propagation reaction, making
the catalyst selective for polycarbonate synthesis.19
Functionalisation of the ligand with tailored groups can

positively aect the catalytic performance of a metal complex.
The presence of a side arm bearing a protonated piperidinium
group on a salen ligand was proposed to prevent cyclic
carbonate formation by protonating the polymer chain in case
it dissociated from the metal centre, thus avoiding the backbiting reaction that would lead to the cyclisation reaction (9 in
Fig. 3 and Table 1).51
Another approach based on the functionalisation of the
ligand aimed at keeping dissociated anionic polymer chains in
the proximity of the metal centre by binding the co-catalyst to
the ligand: cobalt salen complexes with bound quaternary
ammonium units (10 in Fig. 3) displayed improved activity and
selectivity for copolymerisation and generated polycarbonates
with very high molecular weight (Table 1).5255
Introducing halide substituents in the ortho-position of
the aromatic rings of the ligands of the bimetallic phenolate
zinc complex 3 (Fig. 1 and Table 1) caused an increase in the
activity of the catalyst in the copolymerisation of cyclohexene
oxide with CO2. The increase was proportional to the electronegativity of the halide (Br o Cl o F), which causes a
Fig. 4 b-Diiminate zinc complexes.
2178
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Fig. 5 Bimetallic zinc anilido-aldimine complex.
decrease in electron density at the metal centre and, thus, an

increase in the binding ability of the metal to the epoxide.56,57
This is in line with the rate-determining step for bimetallic zinc
complexes being the activation of the epoxide rather than the
insertion of CO2 (see mechanism 2.2.c). The same trend is
followed by the bimetallic zinc complexes 2 in Fig. 1, which
showed a decrease in catalytic activity upon variation of the
substituent in the para-position on the aromatic ring from an
alkyl group to an electron-donating methoxy group.58
Modifying a ligand towards optimum catalytic performance of the metal complex often requires a ne tuning. This
is exemplied by the b-diiminate zinc complexes (Fig. 4 and
Table 1), for which the substituents at both the N-aryl ring and
the diimine backbone can inuence strongly the catalytic
behaviour of the complex.8,59 For the b-diiminate zinc acetate
complexes, the N-aryl groups should provide sucient steric
bulk to prevent the formation of tightly-bound, inactive
dimeric species, but should also not be so bulky to generate
encumbered, inactive monomeric species. The most active
species were shown to have intermediate features, allowing
the formation of highly-active loosely-bound dimers (12 in
Fig. 4).30 The introduction of electron-withdrawing groups
(e.g. CN, CF3, 13eg in Fig. 4) on the diimine backbone
leads to a relevant enhancement of the catalytic activity in the
copolymerisation reaction.60 However, the presence of more
electron-withdrawing groups is detrimental to the activity (13h
in Fig. 4), probably because the consequently increased Lewis
acidity of the metal centre results in too strong metaloxygen
bonds (see Section 3.1.a).19
Another example of the electronic and steric eect of the
substituents is provided by bimetallic zinc anilido-aldimine
complexes as catalysts for the copolymerisation of cyclohexene
oxide and CO2 (Fig. 5 and Table 1). Bulky groups on the
aromatic rings can have either a positive or negative eect on
the activity according to their position within the complex.
An increase in activity was also observed using electronwithdrawing uorine substituents, whose proposed double
role is to decrease the electron density at the metal centres,
increasing the ability to bind CO2 and epoxide, and to decrease
the basicity of the ligand and, thus, the sensitivity of the
complex to protic impurities.61,62
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Two of the most widely studied types of ligands in metal

complexes employed as catalysts for the reaction of carbon
dioxide with epoxides are the porphyrin and the salen ligands
(see Section 2). Both provide complexes with a planar structure
and tetradentate coordination of the metal centre. Depending
on the nature of the metal, these complexes may accommodate
also ligands in the two axial positions. These axial ligands can
be neutral or anionic, they are generally labile and, therefore,
can be displaced during the reaction.
Generally, the rate-determining step of the coupling reaction
between epoxides and CO2 is the epoxide ring-opening by a
nucleophile. This can be an external nucleophile or a nucleophile belonging to the catalyst. In the case of salen or porphyrin
complexes, the nucleophiles occupy the axial sites in the
complex (see mechanisms 2.1.b and 2.2.a). Nucleophile ligands
in axial position may have two roles: as a nucleophile that
dissociates from the metal centre to attack the epoxide substrate
and open its ring; or as a nucleophile that decreases the strength
of the bond between the metal and the nucleophile in the trans
axial position (see mechanisms in Section 2). The features of the
axial ligand can aect both the degree of epoxide conversion
and the selectivity of the reaction. To achieve good activity, the
axial ligand should not be too strongly bound to the metal, so
that is can dissociate from it, while still being a suciently good
nucleophile to attack the epoxide. If the axial ligand is able to
dissociate easily from the complex, it might also be a good
leaving group from the metal-bound carbonate intermediates,
thus facilitating the back-biting reaction and favouring cyclic
carbonate production (see Scheme 2). On the other hand,
a nucleophile with poor leaving ability can suppress the
formation of cyclic carbonates and increase the selectivity
towards polycarbonates. If a complex with a nucleophile in
the axial position is used in combination with a co-catalyst
providing a second nucleophilic species to the reaction, the
eect of the axial ligand is tightly related to the nature of
the co-catalyst (see mechanism 2.1.b). These considerations
indicate that a ne tuning is generally required for nding the
optimum axial ligand for the desired reaction (cycloaddition
or copolymerisation).
For example, the selectivity between polymeric and
cyclic carbonate in the reaction of propylene oxide with CO2
catalysed by a cobalt salen complex in combination with
Bu4NBr as co-catalyst was dramatically increased (from 3 to
78%) by changing the axial ligand (X) of the complex from
acetate to 2,4-dinitrophenolate (DNP) (5b in Fig. 2).63 When the
same complex was used as catalyst with bis(triphenylphosphine)iminium chloride [(PPN)Cl] as co-catalyst, a high selectivity towards
polycarbonate was observed also with axial groups that gave low
selectivity with Bu4NBr.45 The reaction rate was only slightly
aected by changes in the axial group, apart from the case in
which this was the non-nucleophilic ClO4, which caused a
complete loss of activity. In another example with the same type
of cobalt salen complex but without any co-catalyst, it was found
that changes in the axial ligand resulted in substantial dierences in
the rate of reaction between propylene oxide and CO2. The activity
decreased in the order X = Br 4 OBzF5 B OAc 4 Cl 4 I,
with a complete selectivity towards the polycarbonate in all
cases.64 This trend was not maintained if the reaction was
carried out in the presence of (PPN)Cl as co-catalyst: in such a
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Fig. 6 Co-catalysts employed in the reaction of CO2 with epoxides.
case, the rates were signicantly higher with all axial ligands,
but the highest turnover was now observed with X = OBzF5
(pentauorobenzoate), while the selectivity towards the polymer
slightly decreased with X = OAc or Br.45,64
3.2
Co-catalysts and non-metallic catalysts
(a) With a variety of metal complex catalysts for the coupling

reaction between epoxides and CO2, the catalytic performance
can be greatly improved by the addition of a Lewis base as
co-catalyst.14,45 If the metal complex does not contain a group
that can act as a nucleophile (e.g. in Zn-salphen, see Section 3.1.b),
the co-catalyst is actually essential to observe any conversion
in the reaction between epoxide and CO2.48 Similarly to the
role of the nucleophilic axial groups in salen complexes (see
Section 3.1.b), the co-catalyst can play two dierent roles: as a
nucleophile that attacks and opens the epoxide coordinated to
the metal centre; or as a nucleophile that coordinates to the
metal centre increasing its electron density and thus weakening
the bond with other nucleophilic species (e.g. the growing
polymer chain) and providing a favourable electronic environment for the insertion of epoxide and CO2 molecules (see
mechanisms in Section 2).
A specic balance between nucleophilicity (towards attack
of the epoxide), coordination ability (towards the metal
centre), and leaving ability (from the carbonate intermediate
species) of the co-catalyst is required for enhancing the activity
and for tuning the selectivity of each dierent metal complex.
The selectivity is often controlled by the leaving ability of the
nucleophile: a poor leaving group will favour the growth of the
polymer chain while a good leaving group will promote
the back-biting reaction with cyclic carbonate production.
Co-catalysts can be neutral (e.g. an organic base) or ionic
(e.g. an ammonium salt), see Fig. 6. With ionic co-catalysts,
both the anion and the cation may inuence the reaction
between CO2 and epoxide.45 For a given anion, the nucleophilicity towards the reagents will be higher if its cation is
bulkier and thus exerts lower ion-pairing electrostatic attraction towards the anion.18
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Fig. 7 Tetraphenylporphyrin metal complexes.
The ratio between co-catalyst and catalyst has been

reported to play a decisive role in determining the selectivity
towards cyclic or polymeric carbonates. A higher ratio of
nucleophile to metal centres can favour the selectivity towards
cyclic carbonate over polycarbonate, because the excess of
nucleophile tends to displace the metal-bound carbonate
intermediate, thereby favouring the back-biting reaction leading
to the formation of the cyclic product.9,14,65 As an example, it
has been found that a co-catalyst/catalyst ratio higher than 2
tends to favour the selectivity towards the cyclic carbonate with
chromium salen complexes.41,47,66
The importance of the use of a co-catalyst is exemplied
by the catalytic behaviour of tetraphenylporphyrin aluminium
complexes (15a in Fig. 7). These aluminium complexes without
co-catalyst promoted the homopolymerisation of propylene
oxide with very little incorporation of CO2 into the polymer
chain. On the other hand, in the presence of 4-(dimethylamino)pyridine (DMAP) as co-catalyst, the alternating copolymerisation
of propylene oxide and CO2 became the dominant reaction.
The proposed role of DMAP is two-fold: it promotes the
insertion of CO2 into the growing polymer chain and increases
the rate of ring opening of the epoxide by the carbonate
intermediate (mechanism 2.1.b).23
Similarly, the cobalt porphyrin complex 15b in Fig. 7 produced
polycarbonate selectively from the reaction of cyclohexene oxide
and CO2 in the presence of DMAP as co-catalyst in a 0.51 ratio
to the complex (Table 1). Under the same reactions conditions,
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but without DMAP, poly(cyclohexene oxide) was the only

product. If the DMAP/complex ratio was increased to 10,
both polycarbonate and cyclic carbonate were produced, in
agreement with what is observed with other types of complexes
(vide supra).67
An example of the eect of the leaving ability of the anion
of the co-catalyst on the selectivity is provided by studies
with the cobalt salen complex 5b (Fig. 2) as catalyst and a
tetrabutylammonium salt (Bu4NY) as co-catalyst in the reaction of propylene oxide with CO2. Changing the anion (Y) of
the co-catalyst to poorer leaving groups, that is from I and
Br to Cl, F or CH3COO, suppressed the back-biting
reaction and thus increased the selectivity towards the polycarbonate. In the case of F and CH3COO this was accompanied
by a signicant decrease in the reaction rate.45,63 The explanation of
this decrease in activity is not straightforward as it requires
considering the possible interactions of the anion with the ammonium cation, with the metal centre and with the reagents.
The same cobalt salen complex 5b (Fig. 2) was employed to
study the role of the steric hindrance of the co-catalyst. It was
proposed that the ideal ionic co-catalyst for achieving high
activity and selectivity in the copolymerisation of carbon
dioxide and epoxides consists of an anion with poor leaving
ability (e.g. Cl, see above) and of a bulky cation (e.g. bis(triphenylphosphoranylide)ammonium, PPN+). For neutral co-catalysts,
sterically hindered strong organic Lewis bases (e.g. 7-methyl-1,5,7triazabicyclo[4.4.0]dec-5-ene (MTBD)) are preferred over other
strong but less bulky organic bases (e.g. N-methylimidazole),
which can strongly coordinate to the cobalt centre, thus making
it catalytically inactive.45
The positive features of bis(triphenylphosphoranylide)ammonium chloride as co-catalyst were also demonstrated
by a study of the copolymerisation of cyclohexene oxide with
CO2 with chromium salen complex 5a (X = Cl) in Fig. 2. The
reaction rate was signicantly increased using (PPN)Cl instead
of N-methylimidazole as co-catalyst. The improvement was
ascribed to the combination of an anionic nucleophile with a
non-interacting cation as PPN+, in which the positive charge
is delocalised over the large cation. With this Cr-salen complex
and this co-catalyst, mechanism 2.1.b, which implies a shorter
initiation time and thus a higher reaction rate, is expected to be
favoured over mechanism 2.2.a.27
Fig. 8 Bimetallic aluminium salen complex.
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A study of the eect of the anion of the co-catalyst used in

combination with a bimetallic aluminium salen complex (16 in
Fig. 8 and Table 1) was performed by carrying out the reaction
of styrene oxide with CO2 in the presence of dierent tetrabutylammonium halides (Bu4NY, with Y = F, Cl, Br, I). In all
cases the reaction was completely selective towards the cyclic
carbonate, but the conversion of the epoxide varied between a
maximum of 62% with Bu4NBr to almost no conversion with
Bu4NF. The overall order of activity was Br 4 I 4 Cl 4 F.68
This somehow peculiar trend can be explained considering
that the catalytic activity of the halide is determined by a
balance between its nucleophilicity and leaving-group ability:
a good nucleophile would favour the initial opening of the
epoxide ring, but it would also be a worse leaving group in the
last step of the reaction, i.e. in the back-biting reaction leading
to the formation of cyclic carbonate. This balance is also
inuenced by the nature of the Lewis acid site, if present,
and by the nature of the cation of the halide salt. Therefore,
dierent catalytic systems can show dierent order of activity
between the halides.18,68 For example, Zn-salphen complexes
(6b in Fig. 2) display higher activity in the synthesis of various
cyclic carbonates with Bu4NI as co-catalyst compared to
Bu4NBr.69 Even for the same catalyst, the order of activity
between halides can be dierent with dierent epoxides: with a
bimetallic iron amine triphenolate complex as catalyst, Bu4NI
led to higher rates of conversion of terminal epoxides compared
to Bu4NBr, while with sterically hindered epoxides Bu4NBr was
more active. This behaviour has been explained on the basis of
the smaller size of Br, which can be advantageous in the
nucleophilic attack of sterically congested epoxides.70
Additionally, also the stability of the tetraalkylammonium
salt during the reaction might play a role in the catalytic
process (see Section 2.2.b).29
(b) Ionic or neutral nucleophilic compounds, similar to those
used as co-catalysts together with metal catalysts, can also be
employed alone as catalysts for the addition of carbon dioxide
to epoxides (see Section 2.3). Examples of catalysts of this type
include ionic liquids, ammonium, pyridinium and phosphonium salts, and strong organic bases.7,71 These non-metallic
compounds can be used as homogeneous catalysts or be
immobilised on a support to generate heterogeneous catalysts.18
These catalytic systems are intrinsically simpler compared to the
binary systems consisting of a metal complex and a co-catalyst.
This facilitates the correlation between their physicochemical
features and their catalytic properties, particularly in the case of
homogeneous systems. Still, more than one reaction mechanism
is possible with non-metallic catalysts (see Section 2.3) and the
reaction rate depends both on the nucleophilicity of the anion
and on the features of the cation. For example when the anion is
a halide, bulkier cations provide weaker electrostatic attraction
to the halide, thus increasing their nucleophilicity towards the
opening of the epoxide ring.18 This implies that the order of
activity between halides of quaternary ammonium salts can
change as a function of the nature of the ammonium cation (see
previous paragraph).68,72,73 The absence of a metallic Lewis
acid in these catalytic systems implies that generally higher
reaction temperatures are needed to achieve a good degree of
epoxide conversion, driving the reaction towards the thermodynamically favoured cyclic carbonates.7
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3.3
Substrate
The rate of reaction and selectivity towards polymeric or cyclic

carbonate formation does not depend only on the features of
the catalytic system, but is also inuenced by the nature of the
epoxide substrate. Both steric and electronic eects play a role.
Steric congestion around the epoxide ring tends to cause a
decrease in conversion rate in the reaction with carbon dioxide.
This steric eect is more likely to hinder the nucleophilic attack of
the epoxide rather than its coordination to the Lewis acid metal
centre.48,69,70,74 This explains the lower conversion degree usually
observed with internal epoxides (e.g. cyclohexene oxide) or
a-disubstituted epoxides (e.g. 1,1-dimethyloxirane) compared to
those of terminal epoxides with a linear alkyl chain (e.g. propylene
oxide, 1,2-epoxyhexane).48,70
Cyclohexene oxide has a higher tendency to form polycarbonate rather than cyclic carbonate compared to other epoxides
such as propylene oxide or styrene oxide. This preference of
cyclohexene oxide for polycarbonate formation is ascribed to the
strain in forming the ve-membered cyclic carbonate ring imposed
by the adjacent cyclohexane ring.14,75 As a consequence, the
synthesis of poly(propylene carbonate) is often accompanied by
the formation of cyclic carbonate while the synthesis of
poly(cyclohexene carbonate) tends to proceed more selectively.
The nature of groups on the epoxide can aect its
tendency to produce preferentially either the cyclic or the
polymeric carbonate. For example, epoxides with electronwithdrawing groups, such as styrene oxide, have a higher
tendency to produce cyclic carbonate compared to aliphatic
terminal or internal epoxides.76 This behaviour has been
explained on the basis of the most likely position at which
the epoxide ring is attacked by a nucleophile, leading to ring
opening (Fig. 9). For terminal epoxides such as propylene oxide, the
nucleophilic attack is considered to occur predominantly at the less
sterically hindered carbon atom of the epoxide ring (b-carbon),9
both due to its higher accessibility and to the electron-donating
eect of the alkyl group. On the other hand, for epoxides such
Fig. 9 Most likely positions for a nucleophilic attack of the ring in

dierent types of epoxides.
as styrene oxide the nucleophilic ring-opening occurs mainly at

the a-carbon as a consequence of the electron-withdrawing
inductive eect of the phenyl group. This can lead, after CO2
insertion, to an intermediate in which the electron-withdrawing
nature of the aromatic ring can favour the back-biting reaction
with formation of cyclic styrene carbonate (Scheme 10).46,76
Similarly, the electron-withdrawing nature of the chloromethyl
group of epichlorohydrin tends to drive the reaction towards the
cyclic carbonate product.77 In the case of propylene oxide, even if
the nucleophilic attack at the b-carbon of the epoxide ring is
favoured, the attack at the a-carbon can occur. This is demonstrated by the generally observed presence of head-to-head and
tail-to-tail connections in the poly(propylene carbonate) chain,
whereas if the nucleophilic attack occurred always at the same
position the polymer would contain exclusively head-to-tail
connections (Fig. 10).23,45 A high percentage of head-to-tail
connections (regioregularity) is desirable as it can increase the
crystallinity and improve properties of the polymer including
thermal resistance, toughness and stiness (see challenge 1).14
The nature of the catalytic system can strongly aect the
regioregularity of the obtained polycarbonate.63,64 Particularly,
it has been suggested that a chiral environment around the metal
centre can promote the regioselectivity of the reaction.46
The nature of the epoxide substrate has a strong inuence
on the properties of the alternating copolymer obtained upon
reaction with CO2. As mentioned in challenge 1, the physicochemical properties of these polycarbonates should be enhanced
in order to grant their applicability. This could be achieved by
increasing the rigidity of the polymer backbone through the
choice of suitable epoxides. Poly(propylene carbonate) has
good mechanical properties but rather low glass transition
temperature (B40 1C), while poly(cyclohexene carbonate) has
higher glass transition temperature (115 1C) but is brittle.
Recently, indene oxide has been introduced as substrate for
the synthesis of a promising polycarbonate, displaying the
highest glass transition temperature (134 1C) reported so far
for alternating copolymers of epoxides and carbon dioxide.14,78
This poly(indene carbonate) is thermally stable up to 249 1C,
which is in the same range as the thermal decomposition
temperature of poly(propylene carbonate) and lower than that
of poly(cyclohexene carbonate) (B300 1C).8,14
Oxetanes represent another class of compounds that has
been recently studied as substrates for the formation of cyclic
and polymeric carbonates upon reaction with CO2.70,79,80
Compared to epoxides, oxetanes are characterised by lower ring
strain, which implies that the ring opening step is more challenging.
On the other hand, binding of the oxetanes to the Lewis acidic
metal centre can be favoured by their higher basicity compared to
epoxides.80 Another main dierence between epoxides and oxetanes
is that for the former the ve-membered cyclic carbonates are
the thermodynamically favoured products, while for the latter
the polycarbonate is thermodynamically more stable than the
six-membered cyclic carbonate.
3.4 Solvent and reaction conditions
Scheme 10 Possible back-biting reactions in the reaction of styrene

oxide with CO2.
2182
(a) In order to achieve optimum performance of the catalytic

system, the contact between all components taking part in the
reaction should be maximised (challenge 4).69 In the case of a
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Fig. 10 Possible epoxide/CO2 connections in polycarbonates.
reaction with a binary homogeneous catalytic system, e.g. a

metal complex and an ammonium salt, this implies trying to
get a homogeneous solution containing CO2, the epoxide, the
catalyst and the co-catalyst. This can be a challenging task, as
these components can cover a rather broad range of polarity.
To complicate the situation, the solubility of CO2 in liquids
depends on its density,81 which increases with increasing
pressure and with decreasing temperature, while the solubility
of the catalyst and co-catalyst in an organic solution generally
increases with temperature. This means that it is dicult to
predict the eect of a change of temperature on the overall
solubility between the components. Moreover, a high degree
of dissolution of CO2 into the organic solution can cause a
decrease in the solubility of the catalytic species and possibly
induce their precipitation.82 In some cases, the catalyst and/or
co-catalyst are not soluble in the epoxide substrate in the
concentration chosen for the catalytic test, and a solvent is
added to the reaction mixture to achieve full dissolution of the
catalytic species. The presence of a solvent does not necessarily
aect the solubility of CO2 into the reaction mixture, but
would always cause a dilution of the solution, thus decreasing
the contact between the reaction components. This can
negatively aect the reaction rate, as demonstrated by the
much higher activity of a Zn-salphen/Bu4NI catalytic system
in a solvent-free, CO2-rich environment compared to that in
CH2Cl2 or other solvents.49,69 This means that if the catalytic
species dissolve in the epoxide at the temperature at which the
reaction will be carried out, the use of any additional solvent
should be generally avoided.
Another example of the importance of the contact between
the reaction components was provided by the synthesis of cyclic
carbonates carried out in imidazolium-based ionic liquids with
varying length of the alkyl chain of the cation (C2 to C8):
choosing ionic liquids bearing a longer alkyl chain and working
under conditions in which carbon dioxide is supercritical led to
enhanced catalytic activity as a consequence of the higher
solubility of epoxides and CO2 in the ionic liquid phase.83
If the desired product of the reaction of CO2 with epoxides
is the polycarbonate, the presence of alcohols or water even in
small amounts should be avoided, as these polar molecules can
react with the growing polymer chain to yield a hydroxylterminated polycarbonate and a metal-alkoxide or metalhydroxide species from which a new polymer chain can grow.
Therefore, these chain transfer reactions limit the number of
repeating units and, thus, the molecular weight of the polymer
products.14 Moreover, it has been reported that the interaction
of water with the metal centre of the catalyst can cause
substantial loss in activity and polymer selectivity.45
(b) CO2 can be in its gas, liquid or supercritical state (i.e. above
its critical point, 31.1 1C, 73.8 bar) under the reaction conditions.
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Performing the catalytic test in supercritical CO2 rather than

with CO2 in the gas phase can be advantageous for maintaining
a good contact between the components participating in the
reaction, particularly if the epoxide substrate has a relatively
low boiling point and would tend to shift to the gas phase at low
CO2 pressure.69
Carbon dioxide dissolves into epoxides but in general the
two species do not form a single phase. On the basis of the
temperature and of the CO2 pressure, the amount of CO2
dissolved can vary signicantly, and in some conditions the
volume of the phase containing the epoxide can expand
sensibly upon CO2 dissolution. Carrying out the reaction in
a reactor with a viewing window can provide useful information on the phase behaviour of the system.69
The eect of CO2 pressure on the catalytic activity and selectivity
was studied using cobalt and chromium salen complexes (Fig. 2) as
catalysts for the copolymerisation of CO2 and epoxides.47,63,84 In
general, it was found that the activity increases with CO2 pressure
until a maximum, after which the insertion of CO2 is not anymore
the rate-limiting step and further increase of the pressure causes
dilution of catalyst and substrate, thus decreasing the reaction rate.
On the other hand, the selectivity towards the cyclic carbonate sideproduct with the Cr-salen catalyst was lower at higher CO2
pressure, possibly because high CO2 concentrations favour the
insertion of this molecule over the back-biting reaction leading to
cyclic carbonate.84 A similar trend of activity as a function of CO2
pressure, with a maximum value at an intermediate pressure and a
dilution eect causing a decrease of activity with increasing CO2
pressure, has been observed with heterogeneous catalysts based on
supported ionic liquids.32,33,36
(c) Since cyclic carbonates are thermodynamically more
stable than polycarbonates, carrying out the reaction of CO2
and epoxides at elevated temperatures can increase the selectivity
towards the formation of cyclic carbonates. On the other hand,
decreasing the reaction temperature will decrease the reaction
rate but can enhance the selectivity towards the polycarbonates:
since the activation energy for the synthesis of polycarbonates
is usually lower than that for the thermodynamically more
favoured cyclic carbonates, a lower reaction temperature can
allow a kinetic control of the reaction, thus favouring the
polycarbonates. This strategy has been employed to steer the
reaction towards polycarbonates with epoxides that would
otherwise tend to give higher selectivity towards the cyclic
carbonate, as those bearing an electron-withdrawing group
(see Section 3.3).76,77
4. Homogeneous vs. heterogeneous catalysts

The next generation of catalysts for the reaction of carbon
dioxide with epoxides should not only display enhanced
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activity and selectivity towards the desired carbonate product

(cyclic or polymeric), but should also full the requirements
for a green, sustainable process. Therefore, research eorts
should be centred on catalytic systems that do not contain
potentially toxic species (such as, e.g., chromium or 4-(dimethylamino)pyridine), are active in the absence of solvent (see
Section 3.4) and can be easily separated from the reaction
products and reused in consecutive runs without loss of
activity (challenge 5). The last feature is essential in order to
develop catalysts that could nd industrial application in the
production of cyclic and polymeric carbonates. On the basis of
these considerations, a shift in the focus of the research from
homogeneous towards heterogeneous catalysis is expected. So
far, heterogeneous catalysts for the reaction of carbon dioxide
with epoxides have been studied less extensively compared to
homogeneous systems. The factors determining the activity
and selectivity of homogeneous catalysts (see Section 3) can
apply to their heterogeneous counterparts, but the design
exibility that is typical of metal complexes is restricted in
the case of heterogeneous catalysts by the requirement of a
material that can be readily recovered and reused. The most
known and widely employed heterogeneous catalyst for the
copolymerisation of CO2 and epoxides is zinc glutarate,
[Zn(O2C(CH2)3CO2)]n.8,14 This zinc dicarboxylate catalyses
the production of poly(propylene carbonate) with high
molecular weight and with only minor contamination from
ether linkages or cyclic carbonate.14 However, its turnover
frequency is signicantly inferior compared to that of the
most active metal complex catalysts.19 The catalytic reaction
catalysed by zinc glutarate has been proposed to follow the
bimetallic mechanism described in Section 2.2.c.20 It has been
suggested that the distance between two neighbouring zinc
centres is crucial in determining the activity of this family of
heterogeneous catalysts. Double metal cyanides (e.g.
Zn3[M(CN)6]2 with M = Fe or Co) are another class of widely
investigated heterogeneous catalysts for the copolymerisation
of CO2 and epoxides.14 However, these catalysts can present
relevant drawbacks, such as low CO2 incorporation in
the polymer chain and the requirement for harsh reaction
conditions. Metal oxides, zeolites and clays have also been
studied as heterogeneous catalysts for the reaction of CO2 with
epoxides, but all these systems suer from one or more serious
limitations such as the requirement for a homogeneous base as
co-catalyst, low activities, need for harsh reaction conditions
in terms of temperature and CO2 pressure, or leaching of the
active species.8587 A totally dierent strategy for preparing a
heterogeneous catalyst for the coupling reaction of CO2
and epoxides consists in immobilising active homogeneous
catalysts on the surface of a support.7,18,85 Typical materials
that can be used as supports are polymers or silica-based
materials, including mesoporous ordered materials with high

specic surface area such as MCM-41 and SBA-15.32,36,88,89
The immobilisation of the catalytically active species should be
performed through robust covalent grafting to the support, in order
to avoid possible leaching of active species during the reaction.88,89
A general drawback of supported catalysts compared to their
homogeneous counterparts is the lower activity due to diusion
limitations of reagents and products between the solution and the
catalyst surface.90 This eect can be minimised by using supports
with suciently large pores, and by tuning the loading of the
supported species. On the other hand, in some cases the support can
play a catalytic role and the activity of the heterogeneous catalyst
can be higher than that of its homogeneous counterpart. For
example, the silica-supported phosphonium salt SiO2-[PrBu3P]Br
is more active than the homogeneous salt catalyst in the synthesis of
cyclic carbonate from CO2 and propylene oxide.91 This result was
ascribed to the presence of surface silanol groups in proximity of the
immobilised salt (Scheme 11). These silanols can act as electrophiles
and interact with the oxygen atom of the epoxide, increasing its
reactivity towards the ring opening by the Br nucleophile with a
similar mechanism to that sketched in Scheme 9 (see Section 2.3).
Among supported catalysts, relatively few examples of immobilisation of organometallic complexes have been reported,
while supported non-metallic catalysts, and particularly ionic
liquids, are receiving growing attention.7,18,85
Future research should aim at designing and preparing
heterogeneous catalysts with improved activity and a good
control of the product selectivity under milder reaction conditions
compared to the high temperatures and CO2 pressures
generally employed with the heterogeneous systems known
so far. This will most probably imply developing bifunctional
heterogeneous catalysts, containing both Lewis acidic metal
centres and nucleophilic species. A promising example in
this direction was provided recently by bimetallic Al-salen
complexes with quaternary ammonium bromides covalently
attached to the salen ligand, supported on amorphous silica or
MCM-41 (Fig. 11).7,92 These materials were tested as heterogeneous catalysts for the reaction of dierent epoxides with
CO2 both in batch and continuous ow reactors. The catalysts
showed good activity, but tended to deactivate upon reuse in the
batch mode, or after prolonged use in the ow mode. The
deactivation was attributed to degradation through dequaternisation of the ammonium salt (see Section 2.2.b) and the catalysts
could be reactivated by treating them with benzyl chloride to
regenerate the quaternary ammonium species.
In the perspective of an industrial application, it is also
important to reduce the costs connected to catalysts production.
This issue could be particularly relevant when developing
heterogeneous catalysts based on metal complexes immobilised
on a support, as the synthesis of many of the most commonly
Scheme 11 Proposed role of silanols in the reaction of CO2 with propylene oxide.
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6. Conclusions
Fig. 11 Supported bimetallic salen complex.
Scheme 12 Direct synthesis of cyclic carbonates and polycarbonates

from alkenes.
employed complexes (see Sections 2 and 3) is very expensive.93

Reduction of the costs could be achieved by using ligands that
require less expensive synthesis procedures, while still leading
to catalysts with a good performance.
5. Direct synthesis of cyclic carbonates and

polycarbonates using alkenes as substrates
The epoxides used as substrates in the reaction with carbon
dioxide are typically prepared by the catalytic oxidation of
alkenes.94,95 The development of a process for the synthesis
of cyclic carbonates and polycarbonates using alkenes as
substrates would be attractive both from the point of view
of sustainability and of industrial application (challenge 6).
Performing the reaction with this single-step route would be
intrinsically safer and involve lower costs, as it would not
require the purication and handling of epoxides, which
are much more toxic than alkenes and carbonates. This
route would require a multifunctional catalyst that is able to
promote the oxidation of alkenes to epoxides and the following
reaction of the latter with CO2 to yield the carbonates
(Scheme 12). Alternatively, separate, non-interfering catalysts
could be employed. The process could be carried out as a onepot reaction or by two consecutive steps, with the addition of
CO2 being performed once the epoxidation is complete. On the
basis of these considerations, it can be foreseen that developing an ecient process for the direct synthesis of organic
carbonates from alkenes will involve challenges both
in catalyst design and process technology. Few studies of
catalysts for the direct synthesis of carbonates from alkenes
have been reported, typically combining known catalysts for
the two separate reactions (oxidation of alkenes and addition
of CO2 to epoxides).7,96 However, these systems are still
far from optimal and future research eorts should aim at
achieving higher activity with truly heterogeneous catalysts,
while minimising the formation of side-products of the
epoxidation reaction, controlling the selectivity towards
the desired carbonate, and using H2O2 or O2 as oxidant for
the conversion of the alkene to the epoxide.
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The use of carbon dioxide as a feedstock for the production of

useful chemicals is a research topic that is receiving growing
attention both in academia and industry. In this context,
the reaction of CO2 with epoxides to produce either cyclic
carbonates or polycarbonates shows a large potential for
application. In this article, the eect of the various components
of the catalytic system and of the reaction conditions on the
reaction rate and selectivity were systematically discussed. This
knowledge is important in the perspective of tackling the various
open challenges that were outlined throughout the article:
(1) Development of polycarbonates that have suitable
properties for applications.
(2) Control of the selectivity of the reaction towards the
desired carbonate (cyclic or polycarbonate).
(3) Improvement of the catalytic activity in order to reach
high turnover frequencies under mild conditions for a broad
range of substrates including sterically hindered and internal
epoxides and oxetanes.
(4) Optimisation of the reaction conditions in order to
maximise the contact between reagents and catalysts.
(5) Development of heterogeneous catalysts that can be
easily separated and reused without loss of activity while being
competitive with the best homogeneous catalysts.
(6) Direct synthesis of cyclic carbonates and polycarbonates
from alkenes.
Achieving these targets will involve research eorts both
from scientic and technological points of view.
The design of novel, enhanced catalysts for the reaction of
CO2 with epoxides is a complex task: many parameters
determine the performance of the catalysts, and these factors
are often strongly interwoven. Therefore, changing the same
parameter can have an opposite eect on dierent catalytic
systems. This implies that the optimisation of the features of a
given catalytic system will generally require a ne tuning of its
dierent components (e.g. metal, ligands, co-catalyst). From
these considerations it becomes clear that rational design of
novel catalytic systems for the reaction of CO2 with epoxides
should be supported by a rich experimental activity. For this
purpose, the use of High-Throughput techniques can be very
benecial as they enable carrying out a large set of catalytic
tests in parallel.97 This approach allows the rapid screening of
libraries of catalysts, and at the same time grants a high degree
of reliability in the comparison of dierent samples, as all
tests can take place simultaneously under exactly the same
conditions of temperature and pressure.36 Experimental work
can be nicely complemented by theoretical calculations,20,41,98
which can provide useful insight into the interaction between
the catalytic species and the reagents, thus helping the rationalisation of the experimental results and the design of new
catalysts and processes.
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Challenges in The Catalytic Synthesis of Cyclic and Polymeric Carbonates

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Cite this: Catal. Sci. Technol., 2012, 2, 21692187

Challenges in the catalytic synthesis of cyclic and polymeric carbonates

Published on 29 June 2012. Downloaded on 18/02/2015 14:06:27.

Received 30th May 2012, Accepted 26th June 2012

Centre for Surface Chemistry and Catalysis, KU Leuven, Kasteelpark

Paolo Pescarmona was born in

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source, but its use as feedstock for the production of valuable

Masoumeh Taherimehr was

Catal. Sci. Technol., 2012, 2, 21692187

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and on the catalytic systems used to promote it, with the

Catal. Sci. Technol., 2012, 2, 21692187

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a comprehensive overview of all homogeneous and heterogeneous

2. Mechanism of the addition of carbon dioxide to

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the same time. The epoxide is typically activated by interaction of

Phenolate metal complexes.

Catal. Sci. Technol., 2012, 2, 21692187

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Fig. 2 Metal complexes with salen and related ligands.

by means of characterisation with various spectroscopic and

The most widely studied type of catalysts for the reaction

Catal. Sci. Technol., 2012, 2, 21692187

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catalysts on a support are receiving increasing attention (see

This type of mechanisms is exemplied by the wide group of

The occurrence of this mechanism has been supported by an

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The addition of CO2 to epoxides can follow a bimetallic

Catal. Sci. Technol., 2012, 2, 21692187

It has been suggested that in this mechanism the co-catalyst,

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can promote the selectivity of the reaction towards the growth

Salts of organic cations have been employed alone as catalysts

stable cyclic carbonate as the main product. The mechanism

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supported ionic liquids, the imidazolium-based ionic liquids

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3. Catalytic activity and selectivity in the synthesis

A rationalisation of the factors determining the activity and

Catal. Sci. Technol., 2012, 2, 21692187

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behaviour of complexes with the same ligand scaold but with

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