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CATALYSIS
REVIEW

Homogeneous CatalysisNew Approaches to


Catalyst Separation, Recovery, and Recycling
Homogeneous catalysts have many attractive properties, such as high selectivities.
However, many homogeneous catalytic systems cannot be commercialized because
of difculties associated with separating the products from the catalyst. Recent
approaches to tackling this problem are reviewed and compared.
Homogeneous catalysts offer a number of
important advantages over their heterogeneous counterparts. For example, all catalytic
sites are accessible because the catalyst is
usually a dissolved metal complex. Furthermore, it is often possible to tune the chemoselectivity, regioselectivity, and/or enantioselectivity of the catalyst.
Despite these advantages, many homogeneous catalytic systems have not been commercialized because of one major disadvantage compared with heterogeneous catalysts:
the difficulty encountered when trying to separate the reaction product from the catalyst
and from any reaction solvent. This problem
arises because the most commonly used separation method, distillation, requires elevated
temperatures unless the product is very volatile. Most homogeneous catalysts are thermally sensitive, usually decomposing below
150C. The thermal stress caused by product
distillation even at reduced pressure will
therefore decompose the often expensive catalyst. Other conventional processes such as
chromatography or extraction also lead to
catalyst loss. The homogeneous reactions that
have been commercialized either involve volatile substrates and products or do not contain
thermally sensitive organic ligands.
The hydroformylation of propene to butanal (1) is carried out in a continuous process
(2) on a scale of 4 1012 to 5 1012 g/year
with volatile Rh/PPh3 catalysts (Ph, phenyl);
the volatile product is distilled directly from
the reaction pot. A more thermally robust
catalyst, [RhI2(CO)2], is used in the manufacture of acetic acid from the carbonylation
of methanol. This catalyst can withstand relatively high temperatures, although in this
case the distillation is carried out in a flash
evaporator at low pressure, outside the reaction chamber, making it a batch continuous
process (3). The use of low pressure during
distillation often causes other problems. Because the catalysts have been optimized for
stability, activity, and selectivity under the
high-pressure reaction conditions, they may
School of Chemistry, University of St. Andrews, St.
Andrews, Fife, Scotland. E-mail: djc@st-and.ac.uk

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undergo undesirable side reactions under the


reduced pressure conditions of the separator.
In some specialized applications, alternative
separation strategies have been commercially
applied, but thesesuch as the removal of
1,4-butanediol, the product of the hydroformylation of allyl alcohol, from the toluene
solvent by washing with water (4)are often
suitable only for a narrow range of reactions.
Many catalysts with highly desirable
properties in terms of activity and selectivity
have therefore not been commercialized for
anything but the most valuable products. To
overcome the separation problems, chemists
and engineers are investigating a wide range
of strategies other than distillation for recycling the catalyst (5, 6). In this article, I aim
to provide an overview of the thinking, methodology, and progress in this area of research
without attempting to be comprehensive. To
allow comparison of the different approaches, I mainly use the hydroformylation of
long-chain alkenes (typically 1-octene, Fig.
1), using rhodium-based catalysts, to yield
aldehydes for the subsequent manufacture
(several billion kilograms per year) of plasticizers, soaps, and detergents.
Rhodium catalysts typically work under
mild conditions (100C, 25 bar), giving good
activity and selectivity (80 to 90%) to the
desired linear (l) aldehyde. Nonetheless, all
commercial plants carrying out this reaction
use cobalt catalysts, which require much
harsher conditions (typically 200C, 100 bar)
and give poorer selectivities (1), because
rhodium catalysts decompose when attempting to distill the product from them. Solving
the product separation problem for the rhodium-catalyzed reaction in an effective and
economically robust way would represent a

major step forward in homogeneous catalysis. The lessons learned from this reaction
will also be applicable to many others and
could have far-reaching consequences.
The new processes under investigation
can broadly be grouped into two types. In
the first, the catalyst is anchored to some
kind of soluble or insoluble support, and
the separation is carried out by a filtration
technique. This type of process is often
referred to as heterogenizing homogeneous
catalysts. The other type involves designing
the catalyst so that it is solubilized in a
solvent that, under some conditions, is immiscible with the reaction product. These
reactions involve two phases and are often
referred to as biphasic systems. A variety of
systems have been designed for these new
separation strategies (Fig. 2).

Supported Catalysts and Filtration


Insoluble supports. Ligands can be anchored
onto solid materials such as inorganic oxides
(often silica) or polymers. If the anchoring is
covalent, it can be robust enough to withstand
the rather harsh conditions of the catalytic
reaction. Because the ligand for binding the
metal resides only on accessible sites of the
solid and can be designed to protrude into the
solvent, all catalytically active sites are available for reaction, allowing rates and selectivities comparable to those obtained with analogous dissolved catalysts to be achieved. The
main problem is that bonds between metal
and ligand are often broken and reformed
during catalytic reactions. If this happens, the
catalyst may break away from the support
and become dissolved. This leaching process leads to loss of activity of the catalyst
when it is recovered by filtration and recycled, or is used with a continuous liquid flow.
Reduced leaching has been observed when
the catalyst was anchored inside the pores of
zeolites (so-called ship-in-a-bottle catalysts)
or of mesoporous solids.

CHO
+ CO + H2

Linear (l)
Branched (b)

CHO

Fig. 1. Hydroformylation of 1-octene.

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David J. Cole-Hamilton

CATALYSIS

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SPECIAL SECTION

Fig. 2. Structures of ligands, ionic liquids, and polyelectrolytes used for separation. See text for various meanings of n, R, and Y.

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CATALYSIS

Homo/Co
(1)
Homo/Co
(40)
Homo*
(1)
Homo*
(1)
Supported
(7)
Supported/scCO2
(10)
Soluble polymer
(12)
Dendrimer
(15)
Supported dendrimer
(18)
Thermoregulated aqueous biphasic
(22)
Fluorous biphasic
(24)
Fluorous biphasic
(25)
ScCO2
(26)
Ionic liquid
(30)
Supported ionic liquid
(31)
ScCO2/ionic liquid
(32) [(35)]
*Propene, which cannot isomerize.

1-Hexene.

Recently, a system for hydroformylation


reactions was reported in which a member of
the highly selective Xantphos family of ligands was derivatized with a hydrocarbon
chain terminating in a triethoxysilyl group (7,
8). This ligand was incorporated into a solgel solution for the production of silica and
the resulting supported ligand, 1 (Fig. 2),
bound to rhodium. This catalyst shows high
activity and selectivity, and a single sample
has been used for a variety of different hydroformylation reactions under widely varying conditions over a period of more than a
year. The catalyst still retains its activity and
selectivity, providing a very rare example
where leaching has been reduced to an acceptable level (8). It can be used in a continuous liquid flow process by incorporating
monoliths of the sol-gel material suitably
loaded with rhodium into the paddles of the
autoclave stirrer (9).
This catalyst has also been applied to the
hydroformylation of 1-octene in a gas-like continuous-flow system (10). The special properties
of supercritical CO2 (scCO2 )gas-like diffusion combined with good solvating power (see
below)were used to provide the medium in
which the substrates and products were flowed
over the catalyst. 1-Octene, CO, and H2 are all
fully soluble in the scCO2, which can reach all
active catalytic sites. The product, nonanal, is
also soluble in scCO2 and is thus removed from
the catalyst in the scCO2 once it is formed.
When the effluent from the reactor is depressurized, CO2 forms a gas while the product is
collected as a liquid. The only separation required is that of product from unreacted starting
material and any by-products. The CO2 can be
recompressed and recycled. Although the yields
in this particular reaction are low, the principle

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None
14
PPh3
PPh3
1
1
3
4
5
6
7
8
8
12
13
13

300
80
15
16
50
170
30
10
67
50
10
20
200
46
100
200

Vinyl acetate.

150
200
95
110
80
90
80
120
45
100
100
70
65
100
100
100

38
20
770
444
287
160
160
1792
25
182
837
4400
430
318
3600
8 (408)

3.2
1.6
2.0
0.8
0.19
n/a
0.03
7.1
0.03
0.3
0.1
8.8
14.2
1.2
n/a
0.12 (6.1)

Branched aldehyde.

2.3
9
8.8
5.3
40
33
nr
13.9
0.05
nr
4.5
6.3
5.5
49
2.4
3.1 (3.2)

50
80
90
83
96
94
nr
86
92
nr
75
81
79
85
71
76 (76)

0.1
1.2
0.3
nr
20
nr
0.12
0.08
0.17
0.005
0.004
2 (0.03)

nr
nr
nr
nr
nr
nr
nr
16
nr
0.01
nr
nr

R, P
R, S?, L
U
R,L
R, S?
S, L, E
E
P
E
S, E?
P, S, E

Leaching measured for styrene.

is exciting because, even if the metal briefly


dissociates from the ligand, it will not dissolve
in scCO2 and leaching will be minimized.
To my knowledge, the only commercial
example of a homogeneous catalyst heterogenized on a solid support is the carbonylation of
methanol using [RhI2(CO)2] electrostatically
bound to an ion exchange resin (11). However,
in this case leaching cannot be avoided. The
plant in Japan therefore uses a guard bed of
fresh ion exchange resin downstream of the
reaction bed to readsorb any [RhI2(CO)2] that
dissolves. After a period of time, the guard-bed
resin, now loaded with rhodium, is cycled to
become the catalyst bed.
Soluble supports. The supports used to
bind the catalyst may also be soluble in the
reaction medium. This has the advantage that
active catalytic sites are distributed throughout the reaction solution. The catalyst architecture can be similar to that of the efficient
homogeneous catalyst that it is trying to mimic. The supports may be soluble polymers
(12, 13). In a recent example, the anions of 2
were partially exchanged by the anions of 3
(n 0). The resulting polyelectrolyte was
used to catalyze the hydroformylation of
1-octene, with the catalyst product separation
being performed by ultrafiltration. Good rates
were obtained and 93% of the catalyst could
be recycled; the losses were attributed to
ligand oxidation during the many manipulations required for the batch process.
Dendrimers are large (2 to 4 nm) tree-like
molecules with a persistent globular shape,
which makes them more suitable for ultrafiltration than soluble polymers, which may
pass through filtration membranes more easily. The identical groups on the periphery of
the dendrimer can form ligands to metal cat-

alysts. The metal-binding groups are usually


on the exterior of the dendrimer but can also
be buried within shape-selective pockets. Because membranes for enzyme ultrafiltration
have channels 1 nm in diameter, they allow
the solvent and product of a catalytic reaction
to pass through but reject the dendrimerbased catalyst. Advantageously, dendrimers
may exhibit bidentate binding (through two
donor atoms on the same dendrimer arm) to
the metal. The chelate (ring-forming) effect
will then ensure that leaching is minimized.
Furthermore, if the metal separates from its
dendrimer-bound ligand, it may be sequestered again rapidly by one of the many identical binding sites nearby.
Despite these advantages, reactions where
ultrafiltration has been attempted have generally shown loss of activity upon recycling
(14). This may not be because of genuine
leaching, but because the membranes are not
designed for use with organic solvents, high
temperatures, and/or high pressures. Suitable
membranes will probably need to be based on
zeolites rather than the much less robust materials that are used for removing enzymes
from aqueous solutions. One rather unexpected advantage of some dendrimers has
emerged, however: They can show much
higher selectivities to desired products than
their small-molecule analogs. For example, a
dendrimer bearing 16 PPh2 groups on its
periphery, 4, gives linear:branched (l:b) ratios
in the hydroformylation of octene of 13.9 :1,
compared with 3.8 :1 for a small-molecule
analog (15).
In one recent study, dendrimer wedges
(molecules that have dendrimer-like properties but only form part of a sphere) were
anchored to beads of silica (16) or a polymer,

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Table 1. Rhodium-catalyzed hydroformylation of 1-octene, using a variety of separation methods and catalyst systems, compared with results from
homogeneous commercial systems (rst four rows). Abbreviations: nr, not recorded; n/a, not applicable; R, low rate; P, high pressure; S, low selectivity to
linear aldehyde; L, high catalyst leaching; U, ultraltration not attempted; E, expensive ligand and/or solvent.
Rate
Linear
Rh loss
P loss
p
T
TOF
(mol
System
Reference Ligand
l:b
aldehyde [mg (mol
[mg (mol Problem
1
(bar) (C) (hour )
dm3
(%)
product)1] product)1]
hour1)

CATALYSIS

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SPECIAL SECTION

5, using approaches developed for solidmore soluble in the organic phase than in
be dissolved, truly homogeneous catalysis
phase organic synthesis (17, 18). They have
water, so that at the reaction temperature all
can occur, because all participants are fully
been used for hydroformylation and can easthe required components are dissolved in the
dissolved in one phase and no phase transfer
ily be removed by conventional filtration.
organic phase. Upon cooling, the phase tranproblems arise. Most metal-containing comThis procedure combines the advantages of
sition is reversed and the catalyst returns to
plexes, particularly those with aryl-containthe controlled environment of the dendrimerthe aqueous phase; the organic phase, now
ing ligands, are poorly soluble in scCO2, the
most commonly used supercritical fluid, but
bound catalyst with the ease of separation of
devoid of rhodium complex, can be decanted.
can be rendered soluble by incorporation of
the supported catalyst. In this application, the
A biphasic system is exploited in the
fluorocarbon chains (8, n 1) (26) or by
metal-binding phosphine groups may be
commercial Shell Higher Olefins Process
using trialkylphosphines (6).
placed at the end of or along the arms of the
(SHOP). The oligomerization of ethene in
Although the supercritical solvent can
dendrimer. Both types of binding allow good
the presence of a specially designed ionic
very simply be removed by decompression
rates for the hydroformylation of styrene and
nickel catalyst is carried out in 1,4-butaneto a gas, this does not overcome the main
related substrates, but dendrimers in which
diol. The very high polarity of the solvent
separation problem: that of the catalyst
the rhodium is more deeply buried show betensures that the medium- to long-chain alkfrom the product. One elegant example
ter recyclability (18).
ene products phase-separate and can be
where this has been achieved is a hydrogeMembranes with even smaller pore sizes
removed by decanting (23).
nation reaction in which the iridium-based
are also being developed. These nanofiltraFluorous biphasic systems. The problem
catalyst 9 is soluble in scCO2 in the prestion membranes rely on the difference in size
of differential solubility experienced in the
ence of the substrate, but precipitates once
between a simple organic molecule and a
aqueous biphasic systems led Horva th to proall the substrate has been used up (27 ). In
metal complex. They still allow solvent and
pose the use of fluorous-organic biphasic sysan alternative process, temperature and
product molecules to pass through, but retain
tems. Fluorous and organic solvents mix at
pressure swings are used to precipitate the
the organometallic catalyst (19). The advanthe typical reaction temperatures used for
catalyst selectively; the
tage of these systems is that
product is then recovered
optimized catalysts can be
Products
by decompression. This
used without modification.
Reactor
Separator
in scCO2
process has been successThis approach has been sucLow density
fully used for hydroformycessfully applied to a system
CO2 gas, which
lation with ligands such as
in which scCO2 is the solis recycled
Reactants (CO, H2
vent. The scCO2 transports
8 (n 1) (26 ).
and alkene) in scCO2
the products through the
Ionic liquids. Ionic liqsolution
At the lower density
membrane while the catalyst
uids
are salts (for example,
the carbon dioxide
remains in the reactor (20).
10) that are liquid at room
cannot dissolve the
aldehyde product.
temperature, or at least at the
Biphasic Systems
reaction temperature. They
Reactants dissolve in
Aqueous biphasic systems.
have an extremely low vapor
The product and CO2
the ionic liquid and
separate cleanly.
One biphasic system that has
pressure and, depending on
react at the rhodium
been commercialized for the
the design of the ionic liqcatalyst.
Aldehyde
hydroformylation of propene
uid, can dissolve or reject
product
recovery
uses as ligand a sodium salt
organic compounds. They
of sulfonated triphenylphos- Fig. 3. Schematic diagram of a continuous-ow hydroformylation reaction in a also dissolve ionic catalysts.
phine (3, n 0) (21) to supercritical uidionic liquid biphasic system.
The first hydroformylation
make the rhodium-based catreactions carried out in ionic
alyst soluble in water. Beliquids used rhodium comcause most organic compounds do not mix
plexes of 3 (n 2). However, conversions
hydroformylation reactions, but they phasewith water, the reaction can be carried out in
were low, probably because the high lattice
separate at room temperature (24). Using
two phases with rapid mixing to ensure maxenergies of the sodium salts make them rather
rhodium complexes of 7 in a mixture of
imum contact between the catalyst and the
insoluble in the ionic liquid (28). More recent
perfluorocyclohexane and toluene, Horva th
substrate. After the reaction, the mixture is
work has shown excellent activity and selecshowed that good rates for hydroformylation
allowed to settle and the product is decanted,
tivity with ligands such as 11 (29) or 12 (30).
of 1-octene could be obtained and that leachleaving the catalyst in the aqueous phase.
The products can be decanted from 10 (R
ing of rhodium into the organic phase was
However, because of the very low solubility
C4H9, Y PF6) or extracted with nonpolar
very limited (4.2% after nine runs). The l:b
organic solvents. For ligand 12, high rates
of long-chain alkenes in water, the rates of
ratio could be high (8 :1), but 10% of the
and selectivities with minimal leaching (5
reaction are too low for commercialization of
starting alkene was lost through isomerizaparts per billion) are obtained in ionic liquid
this process for the production of detergenttion. Even higher rates can be obtained if the
10 (R C4H9, Y PF6), and it is possible to
range aldehydes.
toluene is omitted and the ligand is replaced
envisage processes involving decanting or
A recently reported approach solves this
by 8 (n 0). In this case, rhodium leaching
extraction of the products into an organic
problem while retaining the advantages of the
is reduced to 0.05% per run (25). The lack of
solvent in a batch continuous mode.
aqueous biphasic systems (22). Instead of
toluene removes the energetic requirement
Another way of using ionic liquids that
being sulfonated, triphenylphosphine was defor fractional distillation to separate the cathas the potential for continuous-flow liquid
rivatized with a polyethylene glycol chain
alyst from a solvent.
operation is to support the ionic liquid as a
(6). At room temperature, the rhodium comSupercritical fluids. Supercritical fluids
film on a solid (such as silica, sometimes
plex of this phosphine is soluble in water but
(compressed gases above their critical temderivatized with molecules similar to the ionnot in organic solvents. Upon heating, howperature) dissolve many low- to mediumic liquid). The catalyst is dissolved in the
ever, the polyether side chains undergo a
polarity organic molecules and are fully misionic liquid film, with the advantage that the
phase transition and the complex becomes
cible with permanent gases. If a catalyst can

surface area of the ionic liquid is greatly


enhanced relative to its volume and the substrate can readily diffuse to the catalyst.
These systems have recently been used for
rhodium-catalyzed hydroformylation with ligands such as 3 (n 0) or 13 (n 0, R
C4H9). The ionic liquids were 10 (R C4H9,
Y PF6 or BF4). Leaching was reduced by
working at low conversions so that the polarity of the substrate/product phase was kept
low to minimize catalyst extraction from the
ionic liquid film (31). One potential disadvantage of using ionic liquids containing
PF6 or BF4 is that they react with traces of
water to give species such as O2PF2 and the
very highly reactive and corrosive HF, which
can destroy the catalyst (32).
Supercritical fluidionic liquid biphasic
systems. An alternative to extracting products
from ionic liquids with organic solvents is to
combine the favorable properties of ionic
liquids with those of supercritical fluids.
scCO2 has been shown to be miscible with
certain ionic liquids (33) and will extract
many organic compounds from ionic liquids
(34), allowing a genuinely continuous process to be developed. An ionic catalyst is
dissolved in the ionic liquid in a stirred tank
reactor. The substrate (alkene for hydroformylation), permanent gases (CO and hydrogen), and scCO2 are then passed into the
reactor either separately or mixed. The reaction takes place and the products flow out of
the reactor dissolved in scCO2, which is decompressed to release the products (Fig. 3).
The CO2 containing any excess CO and H2
can be recompressed for an emissionless and
continuous process that requires no separation of the product from the solvent. The first
demonstration of such a system was in hydroformylation (32) and showed rather low
rates, but these have been much improved by
using ligand 13 (n 2, R C3H7) and an
alternative ionic liquid, 10 [R C8H17, Y
(CF3SO2 )2N] (35). The approach has also
been used for hydrovinylation of styrene (36)
(but using CO2 below its critical temperature),
for Wacker oxidation (37) reactions, and for
kinetic resolution using enzymes (38, 39).

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Conclusions
A number of innovative solutions to the problem of separation of catalysts from products
in homogeneous catalytic reactions have
been proposed and demonstrated (Table 1)
(1). Some are genuinely continuous with
built-in product separation; others can be carried out in batch continuous mode, with the
separation being carried out in an external
chamber by a nondistillation process.
The question of which of these processes
should be commercialized cannot be answered
at present. All of the processes have some
disadvantages, and most of them do not yet
show the activity required for commercial application. The catalyst, solvent, or process may
be very expensive, catalyst leaching may be too
high, the solvent or ligand may be too expensive, or the pressure may be too high. Many
approaches show considerable promise, but
few detailed cost analyses have been carried
out. They will be essential before any commercialization can be contemplated. An important
property of some of the processes may be reduced environmental impact, as a result of recycling most of the components and getting
away from volatile organic solvents with their
polluting properties. The environmental impact
of some solvents (fluorous, ionic liquid) is,
however, still unknown.
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separation and the recovered catalyst is returned to
the reactor. In batch processes, the reaction is carried
out in a sealed vessel and the work-up involves
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14 MARCH 2003 VOL 299 SCIENCE www.sciencemag.org

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SPECIAL SECTION

CATALYSIS

Homogeneous Catalysis--New Approaches to Catalyst Separation,


Recovery, and Recycling
David J. Cole-Hamilton (March 14, 2003)
Science Translational Medicine 299 (5613), 1702-1706. [doi:
10.1126/science.1081881]

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