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26
TOPICS
&
Introductory concepts
&
&
&
&
&
&
787
Self-study exercises
Fig. 26.1 A schematic representation of the reaction prole of
a reaction without and with a catalyst. The pathway for the
catalysed reaction has two steps, and the rst step is rate
determining.
catalysed route has a characteristic Gibbs energy of activation, G , but the step that matters with respect to the rate
of reaction is that with the higher barrier; for the catalysed
pathway, the rst step is the rate-determining step. (See
Box 26.1 for the relevant equations for and relationship
between Ea and G .) Values of G for the controlling
steps in the catalysed and non-catalysed routes are marked
in Figure 26.1. A crucial aspect of the catalysed pathway is
that it must not pass through an energy minimum lower
than the energy of the products such a minimum would
be an energy sink, and would lead to the pathway yielding
dierent products from those desired.
Catalytic cycles
A catalysed reaction pathway is usually represented by a
catalytic cycle.
A catalytic cycle consists of a series of stoichiometric
reactions (often reversible) that form a closed loop; the
catalyst must be regenerated so that it can participate in the
cycle of reactions more than once.
k0 T G =RT
e
h
788
Fig. 26.2 Catalytic cycle for the Wacker process; for simplicity, we have ignored the role of coordinated H2 O, which replaces Cl
trans to the alkene.
26:1
26:2
The next step involves nucleophilic attack by H2 O with loss
of H ; recall that coordinated alkenes are susceptible to
nucleophilic attack (see equation 23.77). In the third step,
2CuCl2
1
2 O2
26:3
Choosing a catalyst
A reaction is not usually catalysed by a unique species and a
number of criteria must be considered when choosing the
most eective catalyst, especially for a commercial process.
Moreover, altering a catalyst in an industrial plant already
in operation may be costly (e.g. a new plant design may be
required) and the change must be guaranteed to be nan-
CH3CH=CH2
CO/H2
CH3CH2CH2CHO
n-isomer
(CH3)2CHCHO
i-isomer
H2
H2
CH3CH2CH2CH2OH
(CH3)2CHCH2OH
26:5
The following ratios are important:
. the n : i ratio of the aldehydes (regioselectivity of the
reaction);
. the aldehyde : alcohol ratio for a given chain (chemoselectivity of the reaction).
789
Ph2P
Ph2P
Ph2P
Ph2P
Ph2P
Ph2P
107.6o
112.6o
N
P(C6H11)3
Cl
Cl
Ru
Cl
Ph
P(C6H11)3
Ru
Cl
Ph
P(C6H11)3
C6H11 = cyclohexyl
(26.1)
(26.2)
790
C2H4
RCM
(ring-closing
metathesis)
ROMP
(ring-opening
metathesis
polymerization)
C2H4
+
ADMET
(acyclic diene
metathesis
polymerization)
R'
ROM
(ring-opening
metathesis)
C2H4
+
R'
CM
(cross metathesis)
Fig. 26.3 Examples of alkene (olen) metathesis reactions with their usual abbreviations.
N
Cu+
N
N
N
Grubbs'
catalyst, 26.1
Topologically, the chemical assembly of a catenand is nontrivial because it requires one molecular chain to be threaded
through another. Molecule 26.3 contains two terminal
alkene functionalities and can also act as a didentate ligand
by using the N,N-donor set.
O
26:6
N
Cu+
N
N
N
X
LnM
CH2
MLn
O
O
MLn
(26.3)
The complex [Cu(26.3)2 ] is shown schematically at the lefthand side of equation 26.6. The tetrahedral Cu centre acts
as a template, xing the positions of the two ligands with the
central phenanthroline units orthogonal to one another.
Ring closure of each separate ligand can be achieved by
treating [Cu(26.3)2 ] with Grubbs catalyst, and the result is
the formation of a catenate, shown schematically as the
product in equation 26.6. The relative orientations of the
two coordinated ligands in [Cu(26.3)2 ] is important if competitive reactions between dierent ligands are to be minimized.
MLn
C2H4
Alkene hydrogenation
The most widely used procedures for the hydrogenation of
alkenes nearly all employ heterogeneous catalysts, but for
certain specialized purposes, homogeneous catalysts are
used. Although addition of H2 to a double bond is thermodynamically favoured (equation 26.7), the kinetic barrier is
high and a catalyst is required to permit the reaction to be
carried out at a viable rate without the need for high
temperatures and pressures.
CH2 CH2 H2 C2 H6
"
G 101 kJ mol
1
26:7
Rh
PPh3
PPh3
(26.4)
26:9
16-electron
CH2O Na+
H2
RhCl(PPh3)3
H
MeO
MeO
26:10
Biologically active compounds usually have at least one
asymmetric centre and dramatic dierences in the activities
of dierent enantiomers of chiral drugs are commonly
observed (see Box 23.6). Whereas one enantiomer may be
an eective therapeutic drug, the other may be inactive or
highly toxic as was the case with thalidomide. Asymmetric
synthesis is therefore an active eld of research.
Asymmetric synthesis is an enantioselective synthesis and its
eciency can be judged from the enantiomeric excess (ee):
jR Sj
100
% ee
jR Sj
where R and S relative quantities of R and S enantiomers.
An enantiomerically pure compound has 100%
enantiomeric excess (100% ee). In asymmetric catalysis, the
catalyst is chiral.
K 1:4 104
26:8
18-electron
Cl
Ph3P
791
See for example: When drug molecules look in the mirror: E. Thall
(1996) Journal of Chemical Education, vol. 73, p. 481; Counting on
chiral drugs: S.C. Stinson (1998) Chemical & Engineering News, 21
Sept. issue, p. 83.
792
Fig. 26.5 Catalytic cycle for the hydrogenation of RCHCH2 using Wilkinsons catalyst, RhClPPh3 3 .
If hydrogenation of an alkene can, in principle, lead to enantiomeric products, then the alkene is prochiral (see problem
26.4a). If the catalyst is achiral (as RhClPPh3 3 is), then the
product of hydrogenation of the prochiral alkene is a
racemic mixture: i.e. starting from a prochiral alkene, there is
an equal chance that the -alkyl complex formed during the
catalytic cycle (Figure 26.5) will be an R- or an S-enantiomer.
If the catalyst is chiral, it should favour the formation of one or
other of the R- or S-enantiomers, thereby making the hydrogenation enantioselective. Asymmetric hydrogenations can be
carried out by modifying Wilkinsons catalyst, introducing a
chiral phosphine or chiral didentate bisphosphine, e.g. (R,R)-
DIOP (see Table 26.2). By varying the chiral catalyst, hydrogenation of a given prochiral alkene proceeds with diering
enantiomeric selectivities as exemplied in Table 26.2. An
early triumph of the application of asymmetric alkene hydrogenation to drug manufacture was the production of the
alanine derivative L-DOPA (26.5), which is used in the treatment of Parkinsons disease. The anti-inammatory drug
Naproxen (active in the (S)-form) is prepared by chiral resolution or by asymmetric hydrogenation of a prochiral alkene
(reaction 26.11); enantiopurity is essential, since the (R)-enantiomer is a liver toxin.
Phenylethene (styrene)
Dodec-1-ene
Cyclohexene
Hex-1-ene
2-Methylpent-1-ene
1-Methylcyclohexene
93.0
34.3
31.6
29.1
26.6
0.6
PPh2
HO2C
H2N
For further data, see: F.H. Jardine, J.A. Osborn and G. Wilkinson
(1967) Journal of the Chemical Society A, p. 1574.
PPh2
H
OH
OH
L-DOPA
(S)-BINAP
(26.5)
(26.6)
793
Table 26.2 Observed % ee of the product of the hydrogenation of CH2 C(CO2 H)(NHCOMe) using Rh(I) catalysts containing
dierent chiral bisphosphines.
Bisphosphine
Ph2P
OMe
H
Me
Me
PPh2
P
N
PPh2
CO2tBu
% ee (selective to
enantiomer R or S)
Ph
PPh2
(R,R)-DIOP
(S,S)-BPPM
(R,R)-DIPAMP
73 (R)
99 (R)
90 (S)
CO2H
CH2
26:12
MeOH CO MeCO2 H
"
MeO
H2
Ru{(S)-BINAP}Cl2 catalyst
(S)-BINAP = (26.6)
H
CO2H
26:11
Me
MeO
Naproxen
Self-study exercise
Which of the following ligands are chiral? For each chiral ligand,
explain how the chirality arises.
tBu
Me
P
Me
(a)
Ph2P
tBu
PPh2
(b)
CO
I
Ph2P
C
O
PPh2
(c)
PPh2
(d)
I
Rh
Me
Ph2P
C
Rh
I
I
O
Me
I
CO
(26.7)
Optimizing manufacturing processes is essential for nancial reasons, and each catalytic process has potential
problems that have to be overcome. One diculty in the
Monsanto process is the oxidation of cis-RhCO2 I2 by
HI (reaction 26.13), the product of which easily loses CO,
resulting in the loss of the catalyst from the system (equation
26.14). Operating under a pressure of CO prevents this last
detrimental step and also has the eect of reversing the
eects of reaction 26.13 (equation 26.15). Adding small
amounts of H2 prevents oxidation of Rh(I) to Rh(III).
794
Table 26.3 Major advantages of the Monsanto process over the BASF process for the
manufacture of acetic acid (equation 26.12) can be seen from the summary in this table.
Conditions
BASF
(Co-based catalyst)
Monsanto
(Rh-based catalyst)
Temperature / K
Pressure / bar
Catalyst concentration / mol dm3
Selectivity / %
500
500700
0.1
90
453
35
0.001
>99
26:13
"
26:14
"
26:16
Fig. 26.6 The Monsanto acetic acid process involves two interrelated catalytic cycles.
795
Fig. 26.7 Catalytic cycle for the TennesseeEastman acetic anhydride process.
3. In Figure 26.7, which step is an oxidative addition?
[Answers: refer to the section on the Monsanto process, and
Section 23.7]
Hydroformylation (Oxo-process)
Hydroformylation (or the Oxo-process) is the conversion of
alkenes to aldehydes (reaction 26.17). It is catalysed by
cobalt and rhodium carbonyl complexes and has been
exploited as a manufacturing process since World War II.
RCHCH2 CO H2
RCH2 CH2 CHO RCHMeCHO
"
linear n-isomer
26:17
branched i-isomer
CHO
7%
CHO
22%
CHO
6%
26:18
796
Fig. 26.8 Competitive catalytic cycles in the hydroformylation of alkenes to give linear (inner cycle) and branched (outer cycle)
aldehydes.
Self-study exercises
1. Interpret the data in equation 26.18 into a form that gives an
n : i ratio for the reaction.
[Ans. 1.9 : 1]
2. Draw out a catalytic cycle for the conversion of pent-1-ene to
hexanal using HRh(CO)4 as the catalyst precursor.
[Ans. see inner cycle in Figure 26.8, replacing Co by Rh]
k / 105 s1
Hex-1-ene
Hex-2-ene
Cyclohexene
Oct-1-ene
Oct-2-ene
2-Methylpent-2-ene
110
30
10
109
31
8
797
Table 26.5 A comparison of the operating conditions for and selectivities of three commercial hydroformylation catalysts.
Temperature / K
Pressure / bar
Regioselectivity n : i ratio
(see equation 26.5)
Chemoselectivity (aldehyde
predominating over alcohol)
HCo(CO)4
HCo(CO)3 (PBu3 )
HRh(CO)(PPh3 )3
410450
250300
3 : 1
450
50100
9 : 1
360390
30
>10 : 1
High
Low
High
Alkene oligomerization
Polymer-supported catalysts
CH2Cl
CH2PPh2
26:20
Li[PPh2]
LiCl
(26.8)
N
+ HCo(CO)4
H Co(CO)4
26:21
Fig. 26.9 Simplied catalytic cycle illustrating the
oligomerization of ethene using a nickel-based catalyst;
L phosphine, X electronegative group.
798
Biphasic catalysis
PPh2
Rh
Rh
Cl
(26.10)
(26.9)
+
NMe3
P
NMe3
+
NMe3
+
(26.12)
Cl
+
NMe3
+
Me3N
Biphasic catalysis addresses the problem of catalyst separation. One strategy uses a water-soluble catalyst. This is
retained in an aqueous layer that is immiscible with the
organic medium in which the reaction takes place. Intimate
contact between the two solutions is achieved during the
catalytic reaction, after which the two liquids are allowed
to settle and the catalyst-containing layer separated by
decantation. Many homogeneous catalysts are hydrophobic
and so it is necessary to introduce ligands that will bind to
the metal but that carry hydrophilic substituents. Among
ligands that have met with success is 26.9: e.g. the reaction
of an excess of 26.9 with Rh2 nbd2 m-Cl2 (26.10) gives a
species, probably [RhCl(26.9)3 ]3 , which catalyses the
hydroformylation of hex-1-ene to aldehydes (at 40 bar,
360 K) in 90% yield with an n : i ratio of 4 : 1. An excess of
the ligand in the aqueous phase stabilizes the catalyst and
increases the n : i ratio to 10 : 1. Much work has been
carried out with the P-donor ligand 26.11 which can be introduced into a variety of organometallic complexes by
carbonyl or alkene displacement. For example, the watersoluble complex HRh(CO)(26.11)3 is a hydroformylation
catalyst precursor; conversion of hex-1-ene to heptanal
proceeds with 93% selectivity for the n-isomer, a higher
selectivity than is shown by HRh(CO)(PPh3 )3 under conventional homogeneous catalytic conditions. A range of alkene
hydrogenations are catalysed by RhCl(26.11)3 and it is
particularly ecient and selective for the hydrogenation of
hex-1-ene.
Biphasic asymmetric hydrogenation has also been developed using water-soluble chiral bisphosphines such as
26.12 coordinated to Rh(I). With PhCHC(CO2 H)(NHC(O)Me) as substrate, hydrogenation takes place with 87%
ee, and similar success has been achieved for related systems.
A second approach to biphasic catalysis uses a uorous
(i.e. peruoroalkane) phase instead of an aqueous phase.
We must immediately draw a distinction between the
higher Cn peruoroalkanes used in uorous biphasic catalysis and the low-boiling CFCs that have been phased out
under the Montreal Protocol (see Box 13.7). The principle
of uorous biphasic catalysis is summarized in scheme 26.22.
SO3 Na+
26:22
P
Na+ O3S
(26.11)
SO3 Na+
799
26:23
"
90% selectivity
Os3(CO)12
26:24
H2
C
P
C
H2
F2
C
F2
C
C
F2
C
F2
CF3
+ other isomers
C
F2
84% selectivity
3
26:25
(26.13)
P
F2
C
C
F2
F2
C
C
F2
CF3
C
F2
(26.14)
Self-study exercises
1. Give an example of how PPh3 can be converted into a hydrophilic catalyst.
2. The ligand (L):
SO3 Na+
Ph2P
PPh2
PPh2
forms the complex [Rh(CO)2 L] , which catalyses the hydrogenation of styrene in a water/heptane system. Suggest how L
coordinates to the Rh centre. Explain how the catalysed reaction would be carried out, and comment on the advantages of
the biphasic system over using a single solvent.
[Ans. see C. Bianchini et al. (1995) Organometallics, vol. 14,
p. 5458]
The majority of industrial catalytic processes involve heterogeneous catalysis and Table 26.6 gives selected examples.
Conditions are generally harsh, with high temperatures and
pressures. Before describing specic industrial applications,
we introduce some terminology and discuss the properties
of metal surfaces and zeolites that render them useful as
heterogeneous catalysts.
We shall mainly be concerned with reactions of gases over
heterogeneous catalysts. Molecules of reactants are adsorbed
on to the catalyst surface, undergo reaction and the products
are desorbed. Interaction between the adsorbed species
and surface atoms may be of two types: physisorption or
chemisorption.
800
Fig. 26.10 (a) Catalytic cycle for the hydrogenation of fumaric acid by H4 Z6 -C6 H6 4 Ru4 2 ; (b) H4 Ru4 core of
H4 Z6 -C6 H6 4 Ru4 2 and (c) H6 Ru4 core of H6 Z6 -C6 H6 4 Ru4 2 , both determined by X-ray diraction [G. Meister et al.
(1994) J. Chem. Soc., Dalton Trans., p. 3215]. Colour code in (b) and (c): Ru, red; H, white.
Technique
AES
EXAFS
FTIR
HREELS
LEED
SIMS
STM
XANES
XRD
XPS (ESCA)
Table 26.6
801
Catalyst system
"
"
Ni on support
Ag on support
PtRh gauzes
H
M
H
M
H
M
26:26
The balance between the contributing bond energies is a factor
in determining whether or not a particular metal will facilitate
bond ssion in the adsorbate. However, if metaladsorbate
bonds are especially strong, it becomes energetically less
The notations (111), (110), (101) . . . are Miller indices and dene the
crystal planes in the metal lattice.
802
(26.15)
(26.16)
Self-study exercise
Propene polymerization by the ZieglerNatta process can be
summarized as follows.
3n
ZieglerNatta
catalyst
n
Comment on the type of polymer produced and the need for selectivity for this form of polypropene.
In isotactic polypropene, the methyl groups are all on the same side of
the carbon chain; the polymer chains pack eciently to give a crystalline
material. Isotactic polypropene is of greater commercial value than the
soft and elastic atactic polymer, in which the Me groups are randomly
arranged. Also of commercial importance is syndiotactic polypropene,
in which the Me groups are regularly arranged on either side of the
carbon backbone.
803
Fig. 26.12 A schematic representation of alkene polymerization on the surface of a ZieglerNatta catalyst; the vacant
coordination site must be cis to the coordinated alkyl group.
Fe
CO + H2
Co
26:27
If petroleum is cheap and readily available, the FT process is
not commercially viable and in the 1960s, many industrial
plants were closed. In South Africa, the Sasol process
continues to use H2 and CO as feedstocks. Changes in the
availability of oil reserves aect the views of industry as
regards its feedstocks, and research interest in the FT
reaction continues to be high.
The product distribution, including carbon chain length, of
an FT reaction can be controlled by choice of catalyst, reactor
design and reaction conditions; the addition of promoters
such as group 1 or 2 metal salts (e.g. K2 CO3 ) aects the selectivity of a catalyst. The exact mechanism by which the FT
reaction occurs is not known, and many model studies have
been carried out using discrete metal clusters (see Section
26.8). The original mechanism proposed by Fischer and
Tropsch involved the adsorption of CO, CO bond cleavage
to give a surface carbide, and hydrogenation to produce CH2
groups which then polymerized. Various mechanisms have
been put forward, and the involvement of a surface-bound
CH3 group has been debated. Any mechanism (or series of
pathways) must account for the formation of surface
H2
C
CH3
H2
C
H2
C
H2
C
H2
C
26:28
CH2CH3
H2
C
CH2CH2CH3
804
H
C
H2
C
CH2
H2
C
H2
C
HC
H2
C
H
C
H 2C
H2
C
CH2
26:30
N(ad)
Catalyst surface
Isomerization
H
C
HC
H2
C
CH3
N(ad)
H
C
H2C
H(ad)
NH(ad)
NH(ad) H(ad)
NH2(ad)
NH2(ad) H(ad)
NH3(ad)
CH3
C
H
26:29
Haber process
Figure 26.13 illustrates the vast scale on which the industrial
production of NH3 is carried out and its growth over the
latter part of the 20th century. In equation 14.19 and the
Fig. 26.13 World production of NH3 between 1960 and 2000. [Data: US Geological Survey.]
NH3(g)
26:31
2SO2 O2 2SO3
805
Catalytic converters
Environmental concerns have grown during the past few
decades (see, for example, Box 9.2), and to the general
public, the use of motor vehicle catalytic converters is well
known. Regulated exhaust emissions comprise CO, hydrocarbons and NOx (see Section 14.8). The radical NO is
one of several species that act as catalysts for the conversion
of O3 to O2 and is considered to contribute to depletion of
the ozone layer. Although industrial processes also contribute to NOx emissions, the combustion of transport fuels
is the major source (Figure 26.14). A typical catalytic
converter is 90% ecient in reducing emissions, accommodating current European regulations which call for a 90%
reduction in CO and an 85% decrease in hydrocarbon and
NOx emissions, bringing combined hydrocarbon and NOx
output to <0.2 g km1 . The toughest regulations to meet
are those laid down in California (the Super Ultra Low
Emissions Vehicle, SULEV, standards).
A catalytic converter consists of a honeycomb ceramic
structure coated in nely divided Al2 O3 (the washcoat).
Fine particles of catalytically active Pt, Pd and Rh are
dispersed within the cavities of the washcoat and the whole
unit is contained in a stainless steel vessel placed in sequence
in the vehicles exhaust pipe. As the exhaust gases pass
through the converter at high temperatures, redox reactions
Shell and Bayer are among companies that have introduced processes
to eliminate industrial NOx emissions: Chemistry & Industry (1994)
p. 415 Environmental technology in the chemical industry.
806
Fig. 26.14 Sources of NOx emissions in the US. [Data: Environmental Protection Agency (1998) NOx : How nitrogen oxides
aect the way we live and breathe.]
2CO O2 2CO2
26:34
2Ce2 O3 O2 4CeO2
26:39
26:35
26:40
26:36
26:37
26:38
"
"
"
"
"
"
"
(26.17)
Si
O
O
O
O
O
(26.18)
Si
Al
Si
Al
Si
807
O
O
O
O
O
H
808
Fig. 26.16 The proton-induced conversion of a cluster-bound CO ligand to CH4 : a cluster model for catalysed hydrogenation of
CO on an Fe surface. Each green sphere represents an Fe(CO)3 unit.
Fe
(CO)3
Fe(CO)3
H
Base
(26.19)
H+, H2
H
Model studies involve transformations of organic fragments which are proposed as surface intermediates, but do
C
C
(OC)3Fe
Fe(CO)3
For further details, see M.A. Drezdon, K.H. Whitmire, A.A. Bhattacharyya, W.-L. Hsu, C.C. Nagel, S.G. Shore and D.F. Shriver (1982)
Journal of the American Chemical Society, vol. 104, p. 5630 Proton
induced reduction of CO to CH4 in homonuclear and heteronuclear
metal carbonyls.
Fe
(CO)3
26:41
Glossary
The following terms have been introduced in this chapter.
Do you know what they mean?
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
q
catalyst
catalyst precursor
autocatalytic
homogeneous catalyst
heterogeneous catalyst
catalytic cycle
catalytic turnover number
catalytic turnover frequency
alkene metathesis
Grubbs catalyst
catenand
catenate
coordinatively unsaturated
asymmetric hydrogenation
prochiral
enantiomeric excess
hydroformylation
chemoselectivity and regioselectivity (with respect to
hydroformylation)
biphasic catalysis
physisorption
chemisorption
adsorbate
ZieglerNatta catalysis
FischerTropsch reaction
catalytic converter
zeolite
Further reading
General texts
B. Cornils and W.A. Hermann (eds) (1996) Applied Homogeneous Catalysis with Organometallic Compounds, WileyVCH, Weinheim (2 volumes) The rst volume covers
catalytic processes used in industry; the second volume
deals with recent developments and specialized processes.
F.A. Cotton, G. Wilkinson, M. Bochmann and C. Murillo
(1999) Advanced Inorganic Chemistry, 6th edn, Wiley Interscience, New York Chapter 22 gives a full account of the
homogeneous catalysis of organic reactions by d-block
metal compounds.
R.J. Farrauto and C.H. Bartholomew (1997) Fundamentals of
Industrial Catalytic Processes, Kluwer, Dordrecht Provides
a detailed account of catalysts and their industrial applications.
G.W. Parshall and S.D. Ittel (1992) Homogeneous Catalysis, 2nd
edn, Wiley, New York Contains an excellent coverage of the
applications of homogeneous catalysis in industry.
809
Homogeneous catalysis
D. Forster and T.W. Dekleva (1986) Journal of Chemical Education, vol. 63, p. 204 Catalysis of the carbonylation of
alcohols to carboxylic acids: a detailed look at the Monsanto
process.
A. Furstner (2000) Angewandte Chemie International Edition,
vol. 39, p. 3012 Olen metathesis and beyond: a review
that considers catalyst design and applications in alkene
metathesis.
F.H. Jardine (1994) Hydrogenation and isomerization of
alkenes in Encyclopedia of Inorganic Chemistry, ed. R.B.
King, Wiley, Chichester, vol. 3, p. 1471.
P.W. Jolly (1982) Nickel catalyzed oligomerization of alkenes
and related reactions in Comprehensive Organometallic
Chemistry, eds G. Wilkinson, F.G.A. Stone and E.W. Abel,
Pergamon, Oxford, vol. 8, p. 615.
H.B. Kagan (1982) Asymmetric synthesis using organometallic
catalysts in Comprehensive Organometallic Chemistry, eds
G. Wilkinson, F.G.A. Stone and E.W. Abel, Pergamon,
Oxford, vol. 8, p. 463.
S.W. Polichnowski (1986) Journal of Chemical Education, vol.
63, p. 204 Catalysis of the carbonylation of alcohols to
carboxylic acids: an account of the elucidation of the
mechanism of the TennesseeEastman process.
G.G. Stanley (1994) Carbonylation processes by homogeneous
catalysis in Encyclopedia of Inorganic Chemistry, ed. R.B.
King, Wiley, Chichester, vol. 2, p. 575 A well-referenced
overview which includes hydroformylation, Monsanto and
TennesseeEastman processes.
I. Tkatchenko (1982) in Comprehensive Organometallic Chemistry, eds G. Wilkinson, F.G.A. Stone and E.W. Abel,
Pergamon, Oxford, vol. 8, p. 101 A detailed account of
hydroformylation (with industrial plant ow diagrams) and
related processes.
T.M. Trnka and R.H. Grubbs (2001) Accounts of Chemical
Research, vol. 34, p. 18 The development of L2 X2 RuCHR
olen metathesis catalysts: An organometallic success story:
an insight into Grubbs catalysts by their discoverer.
Heterogeneous catalysis
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review of structures, properties and applications of zeolites.
F.H. Ribeiro and G.A. Somorjai (1994) Heterogeneous
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general introduction to concepts and catalyst design.
Industrial processes
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Covers both homogeneous and heterogeneous catalysis,
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810
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Biphasic catalysis
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new industrial technology.
Problems
26.1
26.2
26.3
26.4
26.5
26.6
26.7
26.8
N
(26.20)
26.9
Chapter 26 . Problems
811
alkenes:
RCH2 CHCH2 E-RCHCHMe Z-RCHCHMe
"
H
(OC)4Os
(26.21)
26.12 Describe briey why a clean nickel surface (fcc structure)
should not be regarded as comprising a perfect closepacked array of atoms. Indicate the arrangements of
atoms that an adsorbate might encounter on the surface,
and suggest possible modes of attachment for CO.
812
Overview problems
26.20 Ligand 26.22 has been designed for use in Ru-based
RO
OR
OR
RO
OR
(26.24)
O
NH
HN
Ph2P
PPh2
R = CH2C6H2-3,4,5-(OC10H21)3
(26.22)
26.21 (a) One proposed method for removing NO from motor
HN
O
C
N
H
N
Rh(CO)2Cl
P
Ph2
O
C
Ph2
P
HN
Rh(CO)2Cl
P
Ph2
Ph2
P
Rh(CO)2Cl
P
Ph2
Ph2
P
O
C
N
(26.23)
can be prepared
by the reaction of [Rh(nbd)(Ph2 PCH2 CH2 PPh2 )]
(nbd 26.24) with two equivalents of H2 . In coordinating
Rh(CO)2Cl
P
Ph2
(26.25)