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Modelling Reactions at the Active Sites of Chiral Ruthenium 54
Catalysts Using Density Functional Theory
By S. A. French
Abstracts 95
New Patents 99
Final Analysis: Casting Platinum Jewellery 102
– A Challenging Process
By Neill Swan
Communications should be addressed to: The Editor, Barry W. Copping, Platinum Metals Review, jmpmr@matthey.com;
Johnson Matthey Public Limited Company, Orchard Road, Royston, Hertfordshire SG8 5HE
DOI: 10.1595/147106707X180891
By S. A. French
Johnson Matthey Technology Centre, Blounts Court, Sonning Common, Reading RG4 9NH, U.K.; E-mail: frencsa@matthey.com
Selectivity is a key success factor in the chiral catalyst technologies market. Understanding
the fundamental processes that occur when a reagent interacts with a homogeneous single
site catalyst, both in its approach and at the active site, is therefore critical to the rational
design of new catalysts. Ruthenium-based asymmetric hydrogenation catalysts have been
considered as part of a collaborative research project. [(S)-XylBINAP-RuH2-(S,S)-DPEN],
first developed by Noyori (1–3), is studied as the parent or prototype model of a series of
efficient hydrogenation catalysts, among them the catalysts based on the P-Phos, PhanePhos
and ParaPhos ligand families (4).
This work addresses homogeneous asymmetric this scheme in mind, a consortium was assembled
hydrogenation of C=O bonds, from ketones to from leading experts (both industrial and academ-
alcohols, which has applications in the industrial ic) in all areas of the workflow. The partners are
production of pharmaceutical intermediates. The the Royal Institution of Great Britain, the
catalyst studied, [(S)-XylBINAP-RuH2-(S,S)- University of Liverpool, the University of
DPEN], is shown in Figure 1. Southampton, Johnson Matthey, AstraZeneca,
Each reaction mechanism may be understood GlaxoSmithKline and Pfizer. The aims of the pro-
in terms of the energies of intermediates and the ject were to implement an evolutionary
roles of ligands and additives, as determined by improvement in ligand/catalyst design strategies:
state-of-the-art computational techniques. The
COMPUTATION ⇔ SYNTHESIS ⇔
knowledge gained will then be exploited for the
design and synthesis of ligands for improved cata- ACCELERATED TESTING
lyst systems. Advances in experimental techniques This computation-guided approach for catalyst
will allow rapid identification of lead ‘designed’ discovery is expected to be more efficient, faster
catalysts by automated parallel screening. With delivering and more revealing on the molecular
aspects of a catalytic cycle than one-at-a-time syn-
thesis or combinatory methodologies, which
usually screen catalysts at random (5); see
Ar2 H H2 Scheme I.
P N H Since the project’s conception there has been a
Ru Ru step change in the ability of industry to perform
high-throughput screening. This acceleration has
P H N H
Ar2 H2 enormously reduced the time required to identify
the right catalyst for any desired transformation
from a library of existing catalysts or ligands. The
Fig. 1 The structure of [(S)-XylBINAP-RuH2-(S,S)- preparation of the library of ligands and catalysts
DPEN], asymmetric hydrogenation catalyst remains, however, the bottleneck in this process.
For example, the selection of the correct sub- reactants and products, and further understanding
stituents at phosphorus in any family of bidentate the need to ‘lock’ conformations of ligands, has
phosphine ligands is largely a matter of trial and led to the capability of performing TS calculations
error, with each component of the family requir- on ‘cut down’ (i.e. simplified) model catalysts, as
ing independent and often time-consuming well as exploring the entry of reactants to a real
synthesis. The design and synthesis of new ligand catalyst system.
backbones is even more time-consuming, and
there is no certainty that the new ligands will be Methods
effective in the desired transformation. The processes of prime interest to us involve
Understanding the factors which govern the rela- the breaking and creation of bonds, which means
tionship between the structure of the ligand and that the electronic structure as well as the molecu-
its efficacy in catalysis will accelerate the process lar structure must be modelled. Traditional
of ligand design by evaluation through computer methods in electronic structure theory, in particu-
simulation (‘in silico’) of a large number of structur- lar Hartree-Fock theory and its descendants, are
al variations, among which only the most based on the complicated many-electron wave-
promising structures will actually be synthesised. function. The main objective of density functional
The project, supported financially by the U.K. theory (DFT) is to replace the many-body elec-
Department of Trade and Industry’s tronic wavefunction as the basic quantity by the
‘Manufacturing Molecules Initiative’ (6), is electronic density. Within this study we have used
focused on two industrially important organic the DFT code DMol3 (8, 9) for both model TS
reactions: (a) the production of chiral alcohols via calculations and constrained optimisations.
the asymmetric reduction of ketones; and (b) C–C All the DFT investigations were performed
bond forming reactions such as the Heck reaction. using the linear combination of atomic orbitals
Molecular modelling has so far focused on approximation, with a double numerical basis set
Reaction (a). Computer simulations have been augmented by polarisation functions (with a 5.5 Å
used, at the molecular-mechanical (7) and, as cut-off). The calculations employed the gradient-
reported here, quantum-mechanical levels, to corrected Perdew-Becker-Ernzerhof (PBE)
investigate the structures of proposed catalysts, exchange-correlation functional. The fine accura-
and to probe the reaction mechanism. cy convergence criteria were used throughout for
Initially it was proposed to use activation ener- both electronic structure and atomic optimisation
gies calculated by considering transition states calculations. The criteria guarantee that the energy
(TS) between reactant and products to compare per bond, bond lengths and angles converge to
the performance of catalysts. However, difficulties approximately 0.1 eV, 0.01 Å and 1º, respectively.
in simulating the reactants and products correctly
caused the TS calculations to fail. Therefore an Constrained Optimisation Calculations
alternative strategy was implemented; a geometric To understand how the reactant molecule
constraint was applied and the reactant brought approaches the metal centre and what restrictions
towards the reactive centre, exploring the pathway are placed on its passage, we have performed a
of the ketone molecule to the active site. large number of simulations to compile a trajecto-
Understanding of the correct relative positions of ry of the path followed, and to compare the
Q1
Q1 Q2
Q2 Q3Q3 Q4
Q4
Product: Product: Product: Product:
(R)-alcohol
(R)-alcohol (S)-alcohol
(S)-alcohol (S)-alcohol
(S)-alcohol (R)-alcohol
(R)-alcohol
plar of the class of asymmetric materials that we reactant must overcome before arriving at the
are interested in understanding. As mentioned active site of the catalyst. The reactant must first
above, initially we focused on understanding the push into a pocket of the catalyst, before arriving
pathway of the reactant to the active site. With at its final alignment. The C=O of the ketone and
this in mind we chose to model the quadrant and the Ru–N bonds lie parallel, thereby maximising
orientation known to lead to the preferred prod- orbital overlap with the hydrogen atoms that
uct. Determining the conformational changes transfer to form the alcohol. The advantage of
forced on the reactant or catalyst during approach computational models is that the changes in geo-
would provide a better understanding of where metrical structure as the ketone approaches can
reactants and products should be sited for TS cal- be observed ‘frame by frame’. It is then possible
culations. The Platinum Metals Review website to follow the trajectory of approach, analyse the
includes an animation (12) showing the final position of the barriers, and view the correspond-
structure from each of the constrained optimisa- ing changes in atomic structure.
tion calculations, starting with a constraint When the reactant enters the pocket of the
(Ru–H - - - C=O) of 8 Å and reducing the separa- catalyst, which begins to occur when the con-
tion between the reactant and catalyst in steps of straint (Ru–H - - - C=O) is between 5 Å and 4 Å,
0.5 Å. It is clear from the animation and subse- the ketone-catalyst system stabilises. This is
quent analysis of the potential energy surface for shown by the total energy of the system decreas-
the pathway (Figures 4 and 5) that we can begin ing, before it has to overcome the largest barrier
to understand the complexity of these systems. between 3.5 Å and 2.75 Å. The barrier is due to
There are two distinct energy barriers that the the interaction of the phenyl ring of the ketone
–3
–5
–7
Constraint, Å
2.25 Å 1.75 Å
with ligands of the catalyst; this interaction Constrained Optimisations: Other Quadrants
increases as the ketone is pulled down onto the Having considered the approach of the reac-
active site. At a constraint of 2.75 Å there is a con- tant along the favoured quadrant, we then
formational change of the reactant, with the addressed the question of whether computational
phenyl ring tilting so that all the carbons of the calculations contain sufficient detail to predict the
ring are no longer in the plane of the other atom- selectivity of a specific catalyst. A catalyst that
ic centres of the ketone. The driving force for this forms products with a high enantiomeric excess
change of conformation is the formation of a (ee) is highly desirable, as these reactions are
hydrogen bond, which holds the ketone as it important in a pharmaceutical context. Here the
moves closer to the active site. The hydrogen physiological reaction to one enantiomer may dif-
bond distance reduces further as the reactant is fer greatly from that to another. Using docking
pulled further towards the catalyst, but the posi- calculations, the aim is to investigate the various
tion of the oxygen atom does not change greatly; arrangements, and thereby provide insight into
the major movement is that of H(NH) of how catalysts may be optimised.
the catalyst. The difference in energy barriers between the
For the reactant to leave the pocket there is different quadrants of approach has the potential
then another barrier, which requires the alignment to provide such discrimination. From Figures 2
of the C=O bond of the ketone to the underlying and 6 it is obvious that two of the possible orien-
Ru–N bond of the catalyst. To this end, the car- tations are sterically ‘favourable’ (quadrants Q1
bon moves further down, changing from sp2 to sp3 and Q3) and two sterically ‘unfavourable’ (Q2 and
hybridisation, until it is in the same plane as oxy- Q4) (1). However, this is not sufficient to under-
gen. This results in the C=O bond lying parallel to stand the selectivity, as Q1 and Q3 lead to (R) and
the Ru–N bond, maximising overlap with the two (S) products, respectively. In fact what this simple
hydrogen atoms to be transferred from the catalyst analysis demonstrates is that the channels that
to the reactant. Simultaneously, the Ru–H bond would be followed by reactants approaching along
elongates; this would contribute to the barrier at a Q2 and Q4 should be closed. However, of most
(Ru–H - - - C=O) constraint of 2.25 Å. importance is to understand why certain catalysts
Q3 Q4
produce much higher ee than others. To this end barrier to approach and would therefore be
we must understand the difference between Q1 expected to show high ee. This is confirmed
and Q3. experimentally where, depending upon ex-
Figure 7 shows clearly that for [(S)-XylBINAP- perimental conditions, an ee of around 97%
RuH2-(S,S)-DPEN], Q1 possesses a much lower is achieved.
40
Normalised at 8 Å
30
X-Q1
X-Q2
20
X-Q3
X-Q4
8 Angs -–kJ/mol
10
–1
0
Relative Energy,RelkJE -mol
-10
-20
-30
-40
Constraint, Å
Constraint (Angs)
Fig. 7 The energy profiles for approach of the reactant to the catalyst along different quadrants. (Numbers are nor-
malised to 8 Å, as here the reactant and catalyst do not interact)
Transition States
To make the best use of available computer Fig. 8 Valence bond representation of transition state in
hydrogenation of acetone
resources, initial TS calculations were performed
on a cut down model of a commercial catalyst
(Figure 2). Acetone was initially considered as the
reactant molecule. From our understanding of the
approach of the ketone to the catalyst, we have
been able to determine a stable configuration for
the reactant. The constrained optimisation calcu-
lations showed that with the ketone hydrogen
bonded to the catalyst, (R2C=O - - - HNH) was
at a minimum energy position when the
(Ru–H - - - C=O) was held at 2.75 Å, with the
hydrogen bond holding the reactant in place. We
further optimised this structure to provide the
starting point for our TS calculations. The product
state has the alcohol physisorbed above the cata-
lyst, and is stabilised by a hydrogen bond between Fig. 9 Molecular configuration for transition state in
hydrogenation of acetone; EA = 3.07 kcal mol–1
COH - - - NH.
The TS forms a six membered ring (Figure 8). genation of acetone is therefore extremely facile,
The hydride bond is elongated from 1.7 Å to proceeding as follows:
1.75 Å. It can be seen from Figure 9 that there is – Incipient bond formation is signalled by the
also a change in the hybridisation of carbon, shortening of the O - - - H distance (from 2.11
which moves from sp2 towards sp3. The TS has a Å to 1.86 Å) in the N–H - - - O hydrogen bond,
(O)C - - - H(Ru) distance of 1.96 Å and and of the Ru–H - - - C distance (from 3.02 Å
(C)O - - - H(NH) of 1.86 Å. It is possible to visu- to 1.95 Å);
alise the imaginary mode that is associated with – Small changes in the same direction are
the TS, and it is found that the two hydrogen observed in the other bond lengths (< 2%).
atoms and carbon are the atomic centres that The structure of the TS, therefore, resembles
move the most. Figure 10 shows the energy pro- much more that of the reactant complex
files for TS searches using the LST and QST [RuH2–acetone] than that of the product complex
calculation methods. [RuH2–iPrOH]. This process is therefore a good
The activation energy that we have calculated is example of the Hammond principle. This states
3 kcal mol–1, which is in agreement with previous that the structure of the transition state will resem-
calculations on similar-sized models of the com- ble that of the product more closely than that of
mercial catalyst, while the calculated reaction the reactant for endothermic processes, whereas
energy is exothermic by 6 kcal mol–1. The hydro- the opposite is true for exothermic reactions. A
–1349.97
–1349.98
–1349.99
–1350.00
–1350.01
–1350.02
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Path Coordinate
Energy vs. LST path 1 Energy vs. CG path 1 Energy vs. QST path 2
Energy vs. CG path 2 Energy vs. QST path 3 Energy vs. CG path 3
Transition state
The Author
Sam French holds a degree in Chemistry with
Medicinal Chemistry from the University of
Warwick, U.K., as well as a Ph.D. from the Royal
Institution of Great Britain (RI). At the RI, he worked
under the supervision of Prof. Richard Catlow FRS.
He held three subsequent postdoctoral research
assistant positions at the RI. All involved large
collaborations with industrial input, specialising in
QM/MM techniques and grid technology in
chemistry and catalysis. He joined Johnson Matthey as a Senior
Scientist in November 2004, to initiate and lead the Computational
Chemistry Group.
By Geoffrey C. Bond
59 Nightingale Road, Rickmansworth WD3 7BU, U.K.; E-mail: geoffrey10bond@aol.com
Although the platinum-gold (Pt-Au) phase diagram shows a wide miscibility gap due to limited
mutual solubility of the components, small particles (< 3 nm) form homogeneous alloys because
all atoms retain their atomic electronic structure, and rehybridisation due to band formation
does not take place. Supported Pt-Au catalysts are often superior to those containing Pt alone
for low-temperature selective oxidations.
Great success has been achieved in a variety of structure often occurs, in which a gold core is sur-
catalytic processes by combining two metallic ele- rounded by a palladium shell (4). The beneficial
ments; examples that spring to mind include the catalytic effect is therefore obtained by the core
platinum-iridium (Pt-Ir) pair for petroleum exerting some kind of modifying influence on the
reforming, the platinum-tin (Pt-Sn) pair for alkane surface atoms. While this has not yet received a
dehydrogenation, and the nickel-gold (Ni-Au) sys- theoretical explanation, the Pt-Au system also
tem for steam-reforming of alkanes (1). The recent poses problems of interpretation that have yet to
upsurge of interest in gold as a catalytic element, be addressed; these are discussed here.
rather than as an inert component that somehow
protects the active one, has led to a series of obser- The Platinum-Gold System
vations on gold-containing bimetallic combi- Unlike the Pd-Au system, the Pt-Au phase dia-
nations (2). In particular, the palladium-gold gram exhibits a very considerable miscibility gap
(Pd-Au) pair has been found more effective than (5), that is to say, the solubility of each metal in the
either component by itself in a number of selective other is strictly limited (Figure 1). In the region of
oxidations, including those of reducing sugars, ambient temperature, the limit of the solubility of
alkenes, and hydrogen (to form hydrogen peroxide
rather than water). The Pt-Au combination has
also proved to be beneficial, performing better 1873
than platinum alone in oxygen reduction at the fuel liquid
cell cathode (3), in selective oxidation of reducing 1673
sugars and other polyols (2), in alkane isomerisa- liquid + alpha
Temperature, K
5/2
3/2
5/2
4d 5d 3/2 6d
–0.3 3/2
platinum in gold is only about 17%, rising to 20% Pt(IV) state is readily accessible, but the Pd(IV)
at 973 K, while the solubility of gold in platinum is state is not (6, 7). It would be an interesting
even less (4% rising to 6%). Between these limits Honours level question for undergraduate students
there will be a mixture of the two saturated solu- to predict the chemistry of eka-platinum.
tions. The contrast with the Pd-Au system is at
first sight surprising, because the palladium and Supported Platinum-Gold Catalysts
platinum atoms are almost identical in size. The In view of this knowledge of the Pt-Au phase
reason for the difference must lie in their different diagram, it is unexpected to find a number of
electronic structures; for palladium the outer elec- papers reporting the preparation of supported cat-
tron configuration is 4d 10, while for platinum it is alysts containing these elements, the very small
5d 9 6s 1. The elevation of a d electron to the s level particles apparently consisting of homogeneous
is a consequence of the relativistic stabilisation of microalloys of the two components. The word
the s and p levels in relation to the d and f levels ‘apparently’ is used advisedly, because very often
(6, 7). Figure 2 shows calculated energy levels for no evidence for alloy formation is provided, and
molybdenum, tungsten and seaborgium, and we the conjunction of the two components is only
may suppose that those for palladium, platinum inferred from the catalytic behaviour. It is how-
and eka-platinum (darmstadtium) would be similar. ever of interest to examine the methods that have
The gap between the s- and d-levels is much been claimed to give homogeneous alloy particles.
reduced with platinum, and this allows its d-elec- They may be classified as follows (2): (a) simulta-
trons to be activated for bonding; this is why the neous or sequential exchange of protons of Y
zeolite with the ethylenediamine complexes of the
two components (8); (b) simultaneous deposition-
precipitation onto TiO2–SiO2 by hydrolysis of a
solution of the mixed chloro-complexes (9); (c)
adsorption of the organometallic complex
Pt2Au4(–C≡CtBu)4 from hexane solution onto
SiO2, followed by calcination to remove the ligands
(10) (this method gives very small particles
(2–3 nm, see Figure 3), shown by energy-dispersive
50 nm analysis to be bimetallic); (d) deposition of Pt-Au
colloids onto carbon (11, 12); (e) use of dendrimer-
Fig. 3 Typical high-resolution electron micrograph of stabilised colloidal particles to make PtAu/SiO2
Pt2Au4/SiO2 catalyst (10) and PtAu/TiO2 catalysts (13). Other proposed
Lattice Parameter, Å
4.04
In a number of cases these methods have been
shown to form small particles (< 5 nm), but it is
significant to observe that the classic method of 4.00
co-adsorption of chloro-complexes from solution,
followed by chemical reduction, gives large parti- 3.96
cles (> 20 nm) with severe phase separation (16).
Co-reduction of solutions of precursors gives first
‘frozen’ solid solutions that are approximately 3.92
0 20 40 60 80 100
homogeneous, but which on heating to 700 K [Au], %
equilibrate into a mixture of two phases; this is
Fig. 4 Vegard’s law plot of the lattice parameters of
consequent on the increase in particle size that the platinum-gold colloids (open points from (11); filled
heating produces (17). The use of alkanethiol- points from (18))
encapsulated colloids to prepare Pt-Au/C catalysts
with various Pt:Au ratios results in particles that differs from that of the isolated atom (19); in the
are mainly 2 ± 1 nm in size, and their homo- free state it is 5d 9 6s 1, but in the solid state it is
geneity has been nicely demonstrated (11) by mea- approximately 5d 9.46s 0.6. This is because, as the
suring their lattice parameters using X-ray number of atoms forming the particle increases,
diffraction. This shows that they exactly obey the electron energy levels of the free atom begin to
Vegard’s law; that is, the lattice parameters are a broaden, then overlap, and finally form a continu-
linear function of composition (Figure 4). This has ous electron band in which rehybridisation between
also been recently confirmed by Rossi (18), at least the s, p and d valence orbitals can readily occur.
for compositions of gold content ≥ 50% (see also The spacing between adjacent energy levels, δ, is
Figure 4). We therefore have very clear evidence given to a first approximation by Equation (i):
that sufficiently small particles can form true solid
δ = EF/n (i)
solutions, but that with larger particles phase
separation is inevitable; they behave as does the where EF is the Fermi energy level and n the num-
macroscopic system. There is no indication in the ber of atoms in the particle. When δ exceeds the
literature of the critical size at which the change of thermal energy k BT (where k B is the Boltzmann
behaviour takes place; for this information we constant), the levels begin to act independently,
need to consider other factors. and the particle then resembles a giant molecule.
Before doing so, however, it is worth noting For EF = 10 eV, a typical value, the critical num-
that many scientists express no surprise that their ber at room temperature is about n = 400, but in
small particles do not behave as the macroscopic the transitional region particles become less metal-
alloy does. This lack of curiosity is unfortunate, to lic at low temperature. There is therefore a
say the least, because knowledge of the bonding in continuous change from non-metallic to metallic
homogeneous alloy particles might help in under- behaviour, without any abrupt transition. Many
standing their catalytic behaviour, and hence in optoelectronic properties vary with particle size,
further improvement. but the minimum size for showing fully metallic
character seems to depend on the technique
Changes in Electronic Structure employed (1). The nature of these changes has
with Particle Size been discussed in a recent book (1).
It has long been appreciated that the electronic One way of looking at the continuous change
structure of platinum in the macroscopic state from non-metallic to metallic behaviour is to
References
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The Author
Combining theory with practice, this intro- important part of the book, and occupy Chapters 3
ductory book provides detailed data obtained dur- to 9. The preparation methods of high purity matri-
ing studies on the refining technologies of the ces for spectroscopic analysis of the precious metals
precious metals in China and abroad. The book has are specially described in Chapter 10. There are two
10 chapters, organised by the refining technologies Appendices which describe the memberships of the
of gold, silver, and the platinum group metals. Shanghai Gold Exchange and refining product
The main physical and chemical properties, standards in the U.S.A. and Russia, respectively.
compounds and complexes of precious metals are
introduced in Chapter 1. The separation methods The Editor of the Book
and technologies of the precious metals are Jianmin Yu is a Professor in the Applied Chemistry Department
reviewed in Chapter 2. The refining technologies, at Kunming University of Science and Technology, Kunming,
Yunnan, 650093, China. He is interested in extraction,
for gold, silver, palladium, platinum, rhodium, iridi- separation, recovery and refining of precious metals.
um, osmium and ruthenium comprise the most E-mail: jianminyu1961@126.com
DOI: 10.1595/147106707X192708
A new scientific event in metathesis chemistry, cross-metathesis (CM) and ring-opening metathe-
the NATO Advanced Study Institute (NATO sis polymerisation (ROMP), have moved far
ASI) on New Frontiers in Metathesis Chemistry: beyond their 20th century boundaries. This has
From Nanostructure Design to Sustainable resulted in a broad diversification towards sustain-
Technologies for Synthesis of Advanced Materials able technologies, and in new perspectives for a
(1) was held in Antalya, Turkey, from 4th to 16th wide range of industrial applications, from produc-
September 2006 (co-directors: Y. Imamoglu and tion of smart, nanostructured materials to the
V. Dragutan). This event is an appropriate sequel manufacture of new pharmaceuticals (6–8).
to the memorable Nobel Prize awarded to During the meeting, recent advances in
metathesis scientists Yves Chauvin, Robert H. metathesis chemistry were disseminated among a
Grubbs and Richard R. Schrock (Stockholm, selected audience of distinguished scientists and
November 2005) (2–4), and the XVIth young researchers. Lectures, discussions and
International Symposium on Olefin Metathesis poster presentations, organised by a Scientific
(Poznan, Poland, June 2005) (5). Committee (Yavuz Imamoglu (Hacettepe
Prominent scientists and young students from University, Turkey), Valerian Dragutan (Romanian
twelve NATO countries (Belgium, Bulgaria, Academy, Romania), Lajos Bencze (University of
Canada, Czech Republic, France, Hungary, Poland, Veszprém, Hungary), Ezat Khosravi (University of
Romania, Spain, Turkey, U.K. and U.S.A.) and six Durham, U.K.) and Kenneth B. Wagener
NATO Partner countries (Armenia, Azerbaijan, (University of Florida, U.S.A.)) in ten scientific
Kazakhstan, Moldova, Russia and Ukraine), inter- main sessions, dealt primarily with novel metathe-
ested in metathesis chemistry convened in Antalya sis catalysts pertaining to the pgms and several
for two weeks under NATO sponsorship. The other late transition metals, and their application to
purpose was to debate on the newest trends in key metathesis reactions or tandem meta-
olefin metathesis and identify future perspectives thesis/non-metathesis processes of environmental,
in this fascinating field of synthetic organic and industrial and commercial relevance. Such
organometallic chemistry, where platinum group metathesis reactions have profound implications in
metals (pgms), especially ruthenium, are playing a materials science, nanotechnology, and also in
key role. organometallic, organic and polymer chemistry.
Olefin metathesis, one of the most efficient
transition metal-mediated C–C bond forming reac- Developments in Ruthenium-Based
tions, has emerged during the last few years as a Catalysts
powerful synthetic strategy for obtaining fine As expected, in lectures on catalyst-related top-
chemicals, biologically active compounds, architec- ics emphasis was placed on the newest
turally complex assemblies, new materials and developments concerning ruthenium-based com-
functionalised polymers tailored for specific uses, plexes of high activity, selectivity and robustness,
including sensors, semiconductors and microelec- popular for their excellent tolerance toward a vari-
tronic devices. Metathesis reactions, such as ety of functional groups. A whole range of
ring-closing metathesis (RCM), enyne metathesis, alkylidene ruthenium complexes, both neutral and
X iPr X
iPr
Ph Ph
Ru C C C Ru
Cl
Cl Ph
PCy3 PCy3
1 2
3 4 5
Ar P N
N N
N P Ru C H
C Ru N N P Ar
H P
N N
P N N P H
Ar C Ru P
N
N N
N
P
Ru C RT
RT
Ar
H N N
P N N P
Ru P P Ru
Ar C C H
P N N
P Ar
H N N
Ru P P
Ru
C
P P P P
Ar Ru Ru C H
H Ar
C C
Ar H Ar H 6
Ar
Ar Ar
n
Ar
H Ar
H C n
n C
H
n Ru Ru C
H C P P
P P Ru
Ru P N N P H
Ar n P P
C N N C n Ar
H Ru P P Ru
N N
P N N P
n C Ru P
N N
N P Ru C H
N N N P
H P
Ar N N
P P H n Ar
N N N N Ru C
n C Ru P N N P
H
P N N N N P
Ru P P Ru
C N C H n
Ar n P N P Ar
H N
Ru P N P
Ru
C
P P P P
Ru C H
n Ru
H
C C n
n H H
Ar Ar
n
Ar n Ar
Ar
7
Balcar (J. Heyrovský Institute of Physical organic synthesis yielding pharmaceuticals and
Chemistry, Academy of Sciences of the Czech natural products (sugars, alkaloids, nucleosides,
Republic). The new directions cited were: amino acids);
(a) Eco-friendly protocols for metathesis catalysts; (e) Chiral catalysts enabling enantioselective meta-
(b)Supported catalysts and novel techniques for thetical pathways in precision synthesis.
immobilisation; In his talk on ‘Molecular Sieves as Supports for
(c) Applying to metathesis at room temperature Metathesis Catalysts’, Balcar described how
the recognised advantages of ionic liquids siliceous sieves (MCM-41 and -48, SBA-15) and
through the creation of recyclable imidazoli- organised mesoporous alumina were successfully
um-tagged catalysts; used in obtaining new catalysts (principally based
(d) CM, enyne and RCM as key reaction steps in on molybdenum and rhenium oxides) and in het-
The Reviewers
EDITED BY T. J. J. MÜLLER (Universität Heidelberg, Germany), Springer, Berlin, Germany, 2006, 339 pages,
ISBN 978-3-540-32958-9, £123.00, €159.95, U.S.$199.00
Cascade reactions, also known as domino reac- components, which in adverse circumstances leads
tions, are multibond-forming processes in which to the sequential one-pot option, is noted. The
the first reaction creates the functionality/geome- development of bicyclopropylidene as a cyclo-
try necessary for the second reaction to proceed, propyl-1,3-diene source in the three-component
and so on. Volume 19 of the Topics in Heck-Diels-Alder processes is well reviewed, as is
Organometallic Chemistry series comprises eight the use of allenes in three-component Heck-Diels-
chapters written by experts in the relevant areas Alder and Heck-1,3-dipolar cycloaddition cas-
and is heavily weighted towards palladium(0)-catal- cades. The latter provide access to a substantial
ysed processes (5 chapters). Additionally, there is array of heterocycles. Catalytic cross-coupling with
an excellent chapter on the Pauson-Khand reac- ensuing thermal 6π-electrocyclisations, which
tion (mainly cobalt catalysis) and on metathesis results in the annulation of 6-membered carbo- or
(ruthenium). heterocyclic rings onto various core rings including
Chapter 1 (by E. Negishi, G. Wang and G. Zhu) [2,2]-paracylcophanes, is well exemplified.
reviews Pd(0)-catalysed cyclisation-carbopallada- A survey of Pd(0)-catalysed cascades involving
tion and acylpalladation cascades. A logical π-allylpalladium(II) species is given in Chapter 3
organisational framework enables systemisation of (by N. T. Patil and Y. Yamamoto), which is essen-
the sprawling literature, and adequate references to tially a review of Yamamoto’s contributions to the
pertinent reviews and early work are provided. The area. The major focus is on π-allyl generation from
role of proximal alkene and alkyne functionalities allylic systems, including vinyl oxiranes, thiiranes,
in facilitating oxidative insertion of Pd(0) into aziridines and 1,3-dienes. Generation of π-allyl
aryl/vinyl C–halogen bonds is noted. Carbopalla- species from allenes is only fleetingly mentioned.
dation comprises the major part of this chapter, The emphasis is on one- and two-component
and the versatility of such processes is amply processes and examples of both carbo- and hetero-
demonstrated by processes involving polyenes, cycle formation are given, including Yamamoto’s
polyenynes, enylallenes and ynylallenes for the three-component Pd(0)-Cu(I)-catalysed triazole
assembly of a bewildering array of fused, bridged and tetrazole syntheses from allylic carbonates,
and spirocyclic ring systems. The majority of trimethylsilyl azide (TMSN3) and an alkyne or
the cascades are one- or two-component pro- nitrile.
cesses involving the formation of up to Metal-promoted cyclisative cascade reactions
five rings. which incorporate Michael addition as a key step
The following Chapter 2 (by P. von Zezschwitz are the focus of Chapter 4 (by G. Balme,
and A. de Meijere) covers sequential and cascade D. Bouyssi and N. Monteiro). The major emphasis
combinations of the Heck reaction with 6π-elec- is on Pd-promoted processes but examples of
trocyclisations or Diels-Alder and 1,3-dipolar copper(I)-, scandium(III)-, yttrium(III)- and
cycloadditions. The importance of the relative rhodium(I)-promoted processes are included. The
rates of reaction of the substrates and of tempera- review is nicely organised and mainly surveys for-
ture in cascade design involving three or more mation of 5- and 6-membered carbocycles and
Heat treatment of platinum-5 wt.% copper (Pt-5% Cu) below 500ºC is known to result in
an ordering transformation which can significantly increase the hardness of the alloy.
Microsample tensile testing of Pt-5% Cu shows that low-temperature heat treatment of
previously cold-worked specimens results in an increase in yield strength and tensile
strength, with a maximum in strength occurring after heat treatment at 300ºC; but ductility
is unchanged.
The mechanical properties of the widely used tion on mechanical properties other than hardness
jewellery alloy Pt-5% Cu have been investigated has not previously been investigated. In this paper
by several researchers (see, for example, (1–3)) for we investigate the effect on the strength and duc-
the cast, cold worked and annealed conditions. It tility of Pt-5% Cu of heat treatments which result
is however not widely known that platinum con- in ordering. The tensile mechanical properties of
taining around 5 wt.% copper undergoes an platinum and its alloys have not been studied
ordering transformation after low-temperature extensively, owing to the costs associated with
heat treatment (4, 5). Recent work in the Centre tensile specimens of conventional (American
for Materials Engineering (6) showed that the Society for Testing and Materials (ASTM)) scale
Pt7Cu ordered phase, which can form after heat (7). These costs can be considerably reduced by
treatment at temperatures as low as 200ºC, can microsample tensile testing, described previously
improve the hardness of Pt-5% Cu. If the alloy is in this Journal (3). Mechanical properties such as
cold worked before heat treatment, the increase in yield strength, tensile strength and ductility can be
hardness after heat treatment is significant. If the measured using specimens just 8 mm in length. In
alloy is first quenched from high temperatures, an the present work the mechanical properties of Pt-
increase in hardness on heat treatment is measur- 5% Cu, before and after heat treatments which
able but not as great. result in ordering, are fully characterised by
Given the widespread use of Pt-5% Cu in plat- microsample tensile testing and hardness testing.
inum jewellery, it is surprising that there is little
information on this phenomenon in the technical Experimental Procedure
literature. The hardness increase for this alloy has Bars (50 g in mass) of Pt-5% Cu were cold
important implications for the manufacture of rolled to reduce thickness by 50%, before
jewellery, since using low-temperature heat treat- homogenising at 1000ºC for 12 hours in an argon
ment as a final step in the manufacture of a atmosphere. A fully recrystallised grain structure
jewellery piece can produce a better finish and resulted after homogenising. Composition and
improved scratch resistance. Conversely, hardness homogeneity were assessed by scanning electron
may be inadvertently increased by heating during microscopy (SEM) and energy dispersive spec-
manufacture, leading to difficulty in subsequent troscopy (EDS). The thickness was then further
working of the piece. An understanding of the reduced by 90%, and specimens were cut from
effect of heating on strength accordingly allows the resulting sheet. The 8 mm long specimens for
optimal planning of the manufacturing route. microsample tensile testing were cut with the long
The effect of the Pt7Cu ordering transforma- axis parallel to the rolling direction. Heat
800
600
400
200
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Engineering Strain
cw cw + 100°C cw + 200°C cw + 300°C cw + 400°C
cw + 500°C cw + 600°C cw + 700°C cw + 800°C cw + 1000°C
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35
Engineering Strain
cw cw + 300°C cw + 1000°C
Hardness, HV100 gf
Strength, MPa
1000 250
800 200
600 150
400 100
200 50
0 0
0 200 400 600 800 1000 1200
Heat Treatment Temperature,°C
300ºC (highest increase in strength) and 1000ºC. fracture) are given in Table I.
Relative to the cold worked condition (90% Figure 4 shows the microstructure of the
reduction in rolling), yield strength and tensile Pt-5% Cu alloy before and after heat treatment.
strength are observed to increase after heat treat- After heat treatment at 300ºC (the temperature
ment at between 100ºC and 500ºC. Heat which resulted in the greatest increase in
treatment at 600ºC and above results in a decrease strength), the heavily deformed and elongated
in strength and an increase in ductility. grains from the cold working are unchanged.
Figure 3 shows the yield strength, tensile After heat treatment at 700ºC, a recrystallised
strength and hardness of Pt-5% Cu as a function grain structure is observed, and after heat treat-
of heat treatment temperature. Strength and hard- ment at 1000ºC grain growth has occurred.
ness consistently increase after heat treatment
between 100ºC and 400ºC, as seen in Figure 1. Discussion
Heat treatment at 500ºC results in little change in Cold work followed by heat treatment below
the properties relative to the cold worked condi- 500ºC results in an increase in the yield strength,
tion; heat treatment at higher temperatures results tensile strength and hardness of Pt-5% Cu. These
in a decrease in strength and hardness. Measured results are consistent with a previous report (6) of
values for hardness, yield strength, tensile an increase in the hardness of this alloy due to an
strength and ductility (percentage elongation after ordering transformation. For this alloy the critical
200 μm 200 μm
(c) (d)
200 μm 200 μm
Values in italics are from References (3) and (6). Note that in Reference (3) heat treatment time is six hours
ordering temperature, Tc, is around 500ºC (4, 6), and Table I show that when strength decreases as
which means that a transformation to an ordered a result of recovery and recrystallisation, ductility
state can be expected to occur as a result of heat increases as expected. Heat treatment of cold
treatment below 500ºC. This does not result in worked Pt-5% Cu below 500ºC, however, can
any change in grain structure relative to the cold result in a significant increase in strength relative
worked state, as seen in Figure 4(b); the observed to the cold worked value, but ductility remains
change in properties thus arises entirely from the unchanged. The ordering transformation which
ordering transformation. occurs below 500ºC accordingly has an unexpect-
Hardness is expected to be proportional to ed effect on tensile properties, in that an increase
yield strength (8); this is observed in the results in strength is achieved without further loss
shown in Figure 3. Hardness measurements alone, of ductility.
however, do not provide a complete characterisa- Heat treatment at temperatures above Tc does
tion of mechanical properties, which requires not result in an ordering transformation. In this
tensile testing. It is of interest to note that, alloy, heat treatment at temperatures above 500ºC
although heat treatment between 200ºC and leads to recovery and recrystallisation, as shown in
400ºC results in very similar hardness increases, Figure 4(c), which results in a decrease in strength.
there is a clear maximum in yield strength and ten- Increasing heat treatment temperature above
sile strength after heat treatment at 300ºC. 700ºC results in grain growth, and a consequent
Generally, ductility is expected to decrease as further decrease in strength and increase in ductil-
strength increases and vice versa: Figures 1 and 2 ity are observed.
The Authors
A one day meeting on the Successful Scale-Up L-2-aminobutyric acid, over 40 different pgm cata-
of Catalytic Processes took place on the 5th lysts were screened for use in the reduction step.
October 2006. Organised by the Applied Catalysis Initially, a Pd/C catalyst was identified as the most
Group of the Royal Society of Chemistry (1), it was promising candidate, but the cost proved to be too
hosted by Davy Process Technology Ltd (2) at high, even with reuse of the catalyst and recovery
Stockton-on-Tees, U.K. In all, almost 60 delegates of the Pd metal. Development of a second genera-
attended the meeting, with over 80% being from tion Pd catalyst enabled the costs to be reduced to
industry. There were a total of six oral presenta- an economically attractive level.
tions, of which three covered work using platinum David Johnson (Lucite International Ltd, U.K.)
group metal (pgm) catalysts, especially palladium. presented a paper which outlined the development
and scale-up of their new route to methyl
Cost-Effective Palladium-Catalysed methacrylate (MMA). This novel process employs
Processes two catalytic reaction steps:
Ian Archer (Ingenza Ltd, U.K.) described the (a) carbonylation of ethene in methanol to produce
scale-up of a novel process for the synthesis of pure methyl propionate, using a homogeneous palla-
enantiomers of amino acids and amines. The dium-phosphine catalyst;
process uses chemo-enzymatic deracemisation to (b)condensation of methyl propionate with
generate a single enantiomer from a racemic mixture formaldehyde over a basic heterogeneous cata-
(3). A biocatalysed enantioselective oxidation is used lyst (Cs/SiO2).
to convert one enantiomer of the amino acid or There were several issues which needed to be
amine to a non-chiral imine, which is then reduced addressed during the scale-up of the overall
non-selectively back to the amine, see Scheme I. process, including product separation and purifica-
In order to develop commercially viable tion issues, catalyst manufacture, and the
processes, Ingenza have needed to develop cost- demonstration of product quality.
effective pgm-catalysed reductions. For example, Although the initial research had identified a
for the stereoinversion of D-2-aminobutyric acid to suitable carbonylation catalyst with a turnover
Scheme I Deracemisation of amino
acids by a chemo-enzymatic
process, using a palladium catalyst
Accumulates
Accumulates
as reductant
Biocatalyst during
during reaction
reaction
biocatalyst
(oxidase)
(oxidase) NH 2
NH 2
R1 CO2H
R1 CO2H
NH 2
Chemocatalyst
chemocatalyst
1 (reductant)
(reductant )
R CO2H
Research into organic light-emitting devices the past six years or so. (Reviews and representa-
(OLEDs) has been intense over the past 20 years, tive papers in this field include References (2–5)).
since the landmark report in 1987 of electrically The book is logically structured, appropriately
generated light emission from aluminium beginning with a description of the science behind
tris(8-hydroxyquinoline) (1). Regarded by many as inorganic LEDs – already very well established –
the next generation of display screen technology, before turning to a sequence of chapters describing
OLEDs may eventually rival liquid crystal displays the physical processes underlying charge injection
and conventional inorganic LEDs, and commer- and light emission in conjugated polymers. This is
cialisation has indeed recently begun. The key followed by more chemistry-oriented chapters
hallmark of research in the field is its interdisciplinar- describing the synthesis and properties of electro-
ity, embracing synthetic chemists, physicists, luminescent polymers, charge-transporting/
physical chemists, and electronic and optical engi- charge-blocking materials and dendrimeric sys-
neers, and elegantly spanning fundamental and tems, and the use of crosslinking strategies in
applied science. materials processing. The final three chapters
This new book, edited by two leading German address hybrid inorganic-organic systems, includ-
polymer chemists, brings together contributions ing a useful discussion of nanocrystalline emission
from a dozen of the leading research groups in the (colloidal quantum dots); promotion of triplet
field, representing all of the aforementioned disci- emission using phosphorescent dyes, such as
plines. The result is a coherent account of the cyclometallated iridium complexes and platinum
fundamental principles behind the science of porphyrins (see Figure 1 for representative struc-
OLEDs and of the materials required for their fab- tures); and organic semiconductor lasers.
rication. The book is not for the novice or the Any new book on such an interdisciplinary sub-
undergraduate student; on the contrary, the major- ject as OLEDs faces the challenge of facilitating
ity of the chapters assume familiarity with the mutual understanding of the different disciplines,
underlying physical concepts, and the book is and aiding scientists from one discipline to gain an
probably aimed primarily at those already working appreciation of the issues facing those tackling the
in the field, or intending to enter into it seriously. subject from a different perspective. The book
Perhaps rather disappointingly for the platinum does achieve this to an admirable extent, although
group metal chemist, coverage of iridium- and some chapters are, not surprisingly, more success-
platinum-based electrophosphorescent dopants is ful than others at doing so; the interested chemist
limited to just one chapter that focuses primarily may find himself at sea with some of the physics
on the triplet energy transfer processes rather than chapters and perhaps vice versa. On the other hand,
on the chemistry. This is despite the fact that their this is simply inevitable given the depth of cover-
development as ‘harvesting agents’ for the other- age: the volume overall is unified in structure and
wise non-emissive triplet states has been a buoyant comprehensive in scope.
and high-profile area of research in the field over The book is well produced, with clear diagrams,
Fig. 1 Structures of some of the platinum group metal electrophosphorescent dopants discussed in the book:
(a) fac-tris(phenylpyridine) iridium, Ir(ppy)3; (b) bis(2-(2′-benzothienyl)-pyridinato-N,C3′)iridium(acetylacetonate),
Ir(btp)2(acac); (c) platinum(II) octaethylporphyrin, PtOEP
many of which are helpfully reproduced in colour. complexes as phosphorescent dopants in Chapter
A few chapters, particularly some of those on syn- 11 does seem something of a lost opportunity. The
thetic aspects such as a key chapter on the inorganic chemist hoping for a survey of the latest
synthesis of electroluminescent polymers, were a developments with respect to this aspect would
little disappointing in that they surveyed little post- need to look elsewhere, and in this context, perhaps
2000 work. Given the rapid progress of the field, a forthcoming review volume edited by Balzani and
surely it is important to ensure that a volume of Campagna on the photophysics of metal complex-
this sort is as up-to-date as possible at the time of es may help to fill the gap (8).
publication. It was also a little surprising to find
that while nine of the twelve chapters employ a Conclusion
common referencing style, three use two other In summary, “Organic Light-Emitting Devices”
styles. Though a minor peccadillo, one might rea- provides a comprehensive, wide-ranging and
sonably have expected a unified style. I was also authoritative account of both the science behind
bemused to read in the publishing and retailing OLEDs and of recent developments in the materi-
publicity accompanying the book that Ching Tang als used to produce them. It will make a valuable
of Eastman Kodak was one of the contributors, contribution to the research field for chemists,
even though there is no contribution from him or physicists and optical engineers alike.
anyone else at Eastman Kodak.
References
Comparison with Other Texts
1 C. W. Tang and S. A. VanSlyke, Appl. Phys. Lett.,
There are few comprehensive books available 1987, 51, (12), 913
on OLEDs. Kalinowski’s recent volume “Organic 2 M. A. Baldo, M. E. Thompson and S. R. Forrest,
Light-Emitting Diodes: Principles, Characteristics Pure Appl. Chem., 1999, 71, (11), 2095
and Processes” (6) is geared more exclusively to the 3 R. C. Evans, P. Douglas and C. J. Winscom, Coord.
Chem. Rev., 2006, 250, (15–16), 2093
physics and engineering aspects and, while compre- 4 A. Tsuboyama, H. Iwawaki, M. Furugori, T.
hensive in its treatment of the fundamental physics, Mukaide, J. Kamatani, S. Igawa, T. Moriyama, S.
is a less tractable work. More closely comparable is Miura, T. Takiguchi, S. Okada, M. Hoshino and K.
Ueno, J. Am. Chem. Soc., 2003, 125, (42), 12971
Shinar’s edited review “Organic Light-Emitting 5 I. R. Laskar and T.-M. Chen, Chem. Mater., 2004, 16,
Devices: A Survey” (7), which covers some materi- (1), 111
al common to the present volume. Nevertheless, 6 J. Kalinowski, “Organic Light-Emitting Diodes:
Müllen and Scherf’s contribution is an altogether Principles, Characteristics and Processes”, Marcel
Dekker, New York, 2005
wider ranging survey, bringing in a more diverse 7 “Organic Light-Emitting Devices: A Survey”, ed. J.
range of systems, and has a fresher feel to it. Yet, Shinar, Springer-Verlag, New York, 2004
from the admittedly biased perspective of a plat- 8 “Photochemistry and Photophysics of Coordination
Compounds”, eds. V. Balzani and S. Campagna, to
inum group metal chemist, the rather cursory be published in “Topics in Current Chemistry”,
treatment of only a very few iridium and platinum Springer, Berlin/Heidelberg, 2007
By Thomas Screen
Reaxa Ltd, Hexagon Tower, Blackley, Manchester M9 8ZS, U.K.; E-mail: thomas.screen@reaxa.com
Perovskites are a large class of minerals, both naturally occurring and synthetically produced,
with important technological applications. In this article, platinum group metal (pgm) perovskites
are introduced as a relatively new catalyst material. Due to their high activity, versatile and
stable structure and low pgm content, they can offer advantages over conventional catalysts.
Some of the typical applications and preparation methods of pgm perovskites are reviewed,
with particular focus on their potential use to address current challenges concerning
autocatalysts, and in organic chemistry.
The role of the support in heterogeneous pgm will deviate from the ideal depending on the con-
catalysis is frequently crucial. The choice of sup- stituent properties (for example, ionic radius,
port (usually from carbons, silicas, aluminas, valence and electronegativity). Fractional incor-
zeolites or other inorganic compounds) can poration of several different elements at specific
influence the selectivity, activity and longevity of sites can be achieved through careful design.
the catalyst. Though catalysts of exceedingly high With non-stoichiometric substitutions, oxygen
efficiency are regularly produced, the long-term ion con- ductivity may be induced by oxygen
stability of the pgm system, especially under vacancies (3). Control of substitution in the per-
harsh conditions, can be a problem. In addition, ovskite matrix is important for tuning the
rising pgm demand and costs are incentives properties of the material. For instance, catalytic
towards achieving lower metal loadings and high- activity is apparently determined primarily by the
er activity. Some of these issues can be addressed species at the B site (4).
using pgm-containing perovskites. This review focuses on methods of prepara-
The perovskite structure is a highly versatile tion of pgm-substituted perovskites, on their
and widespread mineral form, of great impor- performance as catalysts, and on their principal
tance in nature and technology (1). They were current and potential uses. As opposed to per-
first described and named by the Russian miner- ovskites used as a support for a metal catalyst,
alogist Count Lev Aleksevich von Perovski, who the main consideration here is of perovskites
discovered the naturally occurring mineral calci- containing the pgm within the mineral lattice; the
um titanate (CaTiO3). The common feature of latter require initial synthesis.
perovskites is the generic structure ABO3, with A
and B drawn from a range of metals, subject to
certain size constraints. The range of possible
cation substitutions is limited by constraints on
thermodynamic stability, as represented in terms A site (La)
B site (Fe, Co)
of the Goldschmidt factor (1). The ideal per- B site (Pd)
ovskite has a cubic structure, with an octahedral Oxygen
configuration of the oxygen atoms at each corner A
Conventional
catalyst
B(OH)2
+ 89 %, 18
18 hh
S I 89%,
S
I B(OH)2
+
MeO 92%,
92 %, 18
18 hh
MeO
H2, 800ºC
Pd(III) Pd(0)
Ar1 Br
Pd(0)
Pd(II) Ar2B(OH)2
1
Ar - Br
Fig. 3 Proposed mechanism for catalytic activity of pgm perovskites in organic synthesis (25)
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14 N. K. Labhsetwar, A. Watanabe, R. B. Biniwale, R. Brennan and S. V. Ley, Chem. Commun., 2003, (21),
Kumar and T. Mitsuhashi, Appl. Catal. B: Environ., 2652
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15 R. Bradow, D. Jovanovic, S. Petrovic, Z. Jovanovic Smith, J. P. Attfield, H. Tanaka, K. Kaneko and S. V.
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The Reviewers
Dave M. Newman, who M. Lesley Wears, who
reviewed Chapter 16, is reviewed Chapter 17, is a
Reader in Information Senior Research Fellow
Storage Materials and at the School of
Technologies at the Engineering, Computer
School of Engineering, Science & Mathematics,
Computer Science & University of Exeter, U.K.
Mathematics, University
of Exeter, U.K.
ABSTRACTS
of current literature on the platinum metals and their alloys
PROPERTIES CHEMICAL COMPOUNDS
Probing the Interface in Vapor-Deposited Reactivity Studies of Rhodium Porphyrin Radical
Bimetallic Pd-Au and Pt-Au Films by CO with Diazo Compounds
Adsorption from the Liquid Phase L. ZHANG and K. S. CHAN, Organometallics, 2007, 26, (3),
D. FERRI, B. BEHZADI, P. KAPPENBERGER, R. HAUERT, K.-H. 679–684
ERNST and A. BAIKER, Langmuir, 2007, 23, (3), 1203–1208 Rh(II) tetramesitylporphyrin, Rh(tmp), reacted with
PVD was used to prepare Pt, Pd, Au, Pt-Au and Pd- ethyl diazoacetate and (trimethylsilyl)diazomethane to
Au films. Their surfaces were characterised by XPS, give Rh(III) porphyrin alkyls. Mechanistic studies
AFM and CO adsorption from liquid CH2Cl2 moni- showed that Rh(tmp) was coordinated with a diazo
tored by ATR-IR spectroscopy. The changes compound, which then underwent a rapid H atom
observed in the IR frequency and in the shape of the abstraction via C–H bond activation to give
CO signals upon adsorption indicated that morpho- Rh(tmp)H. This subsequently reacted with a second
logical changes occur in the Pd films when decreasing molecule of the diazo compound in the rate-deter-
the film thickness from 2 to 0.2 nm and when intro- mining step to give Rh(tmp) alkyl and N2.
ducing a 1 nm Au film. The Pt-Au surfaces were less
sensitive toward CO adsorption. Structural and Magnetic Study of N2, NO, NO2, and
SO2 Adsorbed within a Flexible Single-Crystal
Electric Field-Induced Modification of Magnetism Adsorbent of [Rh2(bza)4(pyz)]n
in Thin-Film Ferromagnets C. KACHI-TERAJIMA, T. AKATSUKA, M. KOHBARA and S.
M. WEISHEIT, S. FÄHLER, A. MARTY, Y. SOUCHE, C. POINSIGNON TAKAMIZAWA, Chem. Asian J., 2007, 2, (1), 40–50
and D. GIVORD, Science, 2007, 315, (5810), 349–351 [Rh2(bza)4(pyz)]n (1) exhibits gas adsorbency. The
The magnetocrystalline anisotropy of ordered FePt structures obtained were characterised as (1)·1.5 N2
and FePd intermetallic compounds can be reversibly (298 K), (1)·2.5 N2 (90 K), and (1)·1.95 NO (90 K)
modified by an applied electric field when immersed under forcible adsorption conditions and (1)·2 NO2
in an electrolyte (propylene carbonate and Na+OH–). (90 K) and (1)·3 SO2 (90 K) under ambient pressure.
A voltage change of –0.6 V on 2 nm thick films The NO inclusion crystal exhibited antiferromagnetic
altered the coercivity by –4.5 and +1% in FePt and interaction between the NO molecules and paramag-
FePd, respectively. The modification of the magnetic netism arising from the NO monomer.
parameters is attributed to a change in the number of
unpaired d electrons. Ordered Arrays of Organometallic Iridium
Complexes with Long Alkyl Chains on Graphite
Hydrogen-Induced Stress Relaxation in Thin Pd J. OTSUKI, T. TOKIMOTO, Y. NODA, T. YANO, T. HASEGAWA,
Films: Influence of Carbon Implementation X. CHEN and Y. OKAMOTO, Chem. Eur. J., 2007, 13, (8),
R. NOWAKOWSKI, P. GRZESZCZAK and R. DUS, Langmuir, 2007, 2311–2319
23, (4), 1752–1758 fac-[Ir(ppy)3] complexes having long alkyl chains
The influence of C impurities on mechanical proper- were shown to form lamellar arrays at a 1-phenyloc-
ties of thin Pd film/H2 has been investigated in situ by tane/HOPG interface. From STM images, it is
AFM. The systems characterised by C incorporation concluded that the molecules align with alkyl chains
from the two opposite sides of thin Pd film (HOPG being interdigitated. Similar lamellar arrays were also
substrate and HC fragments deposit from a gas-phase obtained at the air/HOPG interface upon drop-cast-
reached by preadsorption of ethylene) are compared. ing of toluene solutions.
During PdHx decomposition, C impurities induce cre-
ation of an organised network of cracks which divides
the continuous film into separated domains. ELECTROCHEMISTRY
Ruthenium–Ligand Complex, an Efficient Inhibitor
Hydrogen Sorption Properties of Ternary of Steel Corrosion in H3PO4 Media
Intermetallic Mg–(Ir,Rh,Pd)–Si Compounds M. BENABDELLAH, R. TOUZANI, A. DAFALI, B. HAMMOUTI and
T. SPASSOV, S. TODOROVA, W. JUNG and A. BORISSOVA, J. Alloys S. EL KADIRI, Mater. Lett., 2007, 61, (4–5), 1197–1204
Compd., 2007, 429, (1–2), 306–310 The effect of a macrocycle Ru complex (1) on the
Mg–(Ir,Rh,Pd)–Si (1) with the highest Mg content corrosion of steel in H3PO4 was investigated.
(Mg15Ir5Si2 with channel-like structure) reveals the Inhibition efficiency (E%) increased with concentra-
highest electrochemical H capacity. Generally the tion of (1). Electrochemical impedance spectroscopy
capacities of (1) studied are low. Refining the particle showed that the dissolution process of the steel
size and microstructure of (1) did not result in any sig- occurs under activation control. Polarisation curves
nificant H-capacity increase. indicate that (1) acts as a cathodic inhibitor.
Stability of the First-Generation Grubbs The Effect of Heat Treatment on Nanoparticle Size
Metathesis Catalyst in a Continuous Flow Reactor and ORR Activity for Carbon-Supported Pd–Co
Z. LYSENKO, B. R. MAUGHON, T. MOKHTAR-ZADEH and M. L. Alloy Electrocatalysts
TULCHINSKY, J. Organomet. Chem., 2006, 691, (24–25), L. ZHANG, K. LEE and J. ZHANG, Electrochim. Acta, 2007, 52,
5197–5203 (9), 3088–3094
Ethylene pretreatment of (PCy3)2Cl2Ru=CHPh (1) An impregnation method was used for the synthe-
prior to cross-metathesis of ethylene and cis-2-butene sis of Pd-Co/C (1), in which NaBH4 was the reducing
to form propylene in a continuous flow reactor (CFR) agent. (1) heat-treated at 300ºC had average particle
produced a direct effect on catalyst deactivation. size of 8.9 nm, and the highest ORR catalytic activity.
Similar pretreatment of (1) with cis-2-butene caused Electrocatalytic ORR activity was also examined in an
far less change in the catalyst activity. Continuous acidic solution containing MeOH. (1) has MeOH tol-
removal of products in the CFR was important for erant capabilities.
separating the effects of catalyst decay and catalyst
deactivation caused by the terminal olefin, propylene.
ELECTRICAL AND ELECTRONIC
FUEL CELLS ENGINEERING
Heterostructured Magnetic Nanoparticles: Their
Deposited RuO2–IrO2/Pt Electrocatalyst for the
Versatility and High Performance Capabilities
Regenerative Fuel Cell Y. JUN, J CHOI and J. CHEON, Chem. Commun., 2007, (12),
Y. ZHANG, C. WANG, N. WAN and Z. MAO, Int. J. Hydrogen 1203–1214
Energy, 2007, 32, (3), 400–404 The recent advances in the development of magnet-
RuO2-IrO2/Pt (1) was prepared by even deposition ic nanoparticles (such as FePt, CoPt3) are reviewed,
of Ir hydroxide hydrate and Ru hydroxide hydrate on with a focus on multicomponent heterostructured
Pt black and calcination in air. The RuO2-IrO2 was nanoparticles including alloys, core–shells, and binary
well dispersed and deposited on the surface of Pt superlattices synthesised via nonhydrolytic methods.
black. URFC with deposited (1) showed better per- Their multifunctionality and high performance capa-
formance than that of URFC with mixed (1) catalyst. bilities are demonstrated for applications in high
Cyclic performance of the URFC with deposited (1) density magnetic storage, catalysis, and biomedical
was very stable during 10 cyclic tests. separation and diagnostics. (94 Refs.)
Pt–Ir–IrO2NT Thin-Wall Electrocatalysts Derived Lithography-Free in Situ Pd Contacts to Templated
from IrO2 Nanotubes and Their Catalytic Activities Single-Walled Carbon Nanotubes
in Methanol Oxidation M. R. MASCHMANN, A. D. FRANKLIN, A. SCOTT, D. B. JANES, T.
C.-C. SHAN, D.-S. TSAI, Y.-S. HUANG, S.-H. JIAN and C.-L. CHENG, D. SANDS and T. S. FISHER, Nano Lett., 2006, 6, (12),
Chem. Mater., 2007, 19, (3), 424–431 2712–2717
Lattice O of IrO2 nanotubes (IrO2NT) was C SWNTs were synthesised from an embedded Fe
removed under high-vacuum thermal annealing to catalyst in a modified porous anodic alumina (PAA)
facilitate nucleation of 3–5 nm Ir grains and subse- template (1). Pd is electrodeposited into (1) to form
quent synthesis of PtIr catalyst on the tube walls. The nanowires. Individual vertical channels of C SWNTs
amount of Ir being reduced, the Ir grain size, and the are created, each with a vertical Pd nanowire back
deposited Pt size influence the surface area and the contact. Further Pd deposition resulted in annular Pd
catalytic activity. Pt-Ir-IrO2NT reduced at 500ºC nanoclusters that form on portions of C SWNTs
exhibited higher activity than Pt-IrO2NT and Pt- extending onto the PAA surface. Two-terminal elec-
IrNT in MeOH oxidation, and also a higher current trical characteristics produce linear I–V relationships,
density than that of PtRu in the high potential region. indicating ohmic contact in the devices.
NEW PATENTS
METALS AND ALLOYS ELECTRODEPOSITION AND SURFACE
Reflective Alloy COATINGS
TANAKA KIKINZOKU KOGYO KK Bright Rhodium Electrodeposition
European Appl. 1,734,140 R. J. MORRISSEY U.S. Appl. 2007/0,012,575
A Ag alloy with excellent reflectance maintenance An electroplating solution for obtaining bright
can be used as a sputtering target. A first dopant white Rh electrodeposits contains a soluble sulfate or
element is chosen from Pt, Pd, Rh, Ru, Ir and Au. A phosphate compound of Rh with excess H2SO4,
second dopant is selected from Cu, Mn, Si, Cr, Ni, H3PO4 or a mixture. One or more N-containing het-
Co, Fe, Sc, Zr, Nb, Mo, Ta, W, In, Sn, Pb, Al, Ca, Ge, erocyclic compounds with at least one N atom in a
Ga, Bi, Sb, Sr, Hf, Gd, Sm, Nd, La, Ce, Yb and Eu. 6-membered aromatic ring, such as pyridine, picoline,
The total concentration of the two dopants is pyrimidine, pyridazine or pyrazine or derivatives
0.01–5.0 at.%. thereof, is added as a brightening agent.