Homogeneous Catalysis—Industrial Applications

Jurgen Falbe and Helmut Bahrmann

Ruhrchemie, AG., Mulheim (Ruhr), West Germany
Translator Hans-Georg Gilde1
Marietta College, Marietta, OH 45750

The use of catalysts with their selective and effective
transformation possibilities appears in a new light as a result
of the increased price of oil, a raw material and an energy
source so important to the chemical industry. While hetero-
geneous catalysts have been used for some time by the
chemical industry, the large chemical processes with homo-
geneous catalysts have been applied only in recent times. Now
more than ever in the development and planning of new pro-
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A central problem in the technical use of catalysts is the
contact-separation. As Table 2 indicates, the homogeneous
catalysts can be separated by distillation, extraction with
chemical decomposition, and subsequent filtration. These
operations are in general not quantitative so that in a con-
tinuing process, in contrast to heterogeneous catalysts, the
return of the catalyst necessitates an additional purification.
The separation and re-use of the catalyst are made addition-

cesses it is important, if both systems are applicable to com-
pare carefully the advantages and disadvantages of both
catalysts.
A comparison of important properties of the two types of
catalysts is found in Table 1. There are some obvious advan-
tages of homogeneous catalysts. First, because surface effects
are lacking, homogeneous catalysts are more effective and
have a higher specificity than heterogeneous catalysts.
Moreover, homogeneous catalysts can be made more repro-
ducibly and with definite stoichiometry and structure. Fur-
thermore, they not only work under milder reaction conditions
than heterogeneous catalysts, but also the constancy of ho-
mogeneous-catalyzed reactions can be sustained better over
a longer reaction interval and the material requirements are
as a rule minimal. The catalyst separation, however, in general
is easier with heterogeneous catalysts.
In spite of these advantages, the homogeneous catalysts
could displace the heterogeneous catalysts only in part. The
important large-scale productions of chemical raw materials
from oil—like hydrocracking in the production of ethylene,
propylene, butylene, and aromatics as well as the reforming
processes—are still exclusively heterogeneously catalyzed.
The reason for this is that to date no one has succeeded in
finding a homogeneous catalyst that sufficiently activates the
C—H bond. Significant future prospects, however, will be in
the chemistry of synthesis gas which is based on coal and will
be greatly expanded in the coming years.
1
Permission to publish a translated version of this article, which was
published originally in Chemie in unserer Zeit, [15, 37 (1931)], was
granted by Verlag Chemie and is hereby gratefully acknowledged. The
translator thanks Mrs. H. C. Gilde and Mrs. J. Dunn for their assistance
in the preparation of the manuscript.
ally difficult by the small catalyst concentrations. Extensive
care must be used to avoid losses since often expensive noble
metals are employed. In summary, however, the advantages
of homogeneous catalysts outweigh the disadvantages because
the greater variety of possible and specifically designed re-
actions promise a bright future.
Industrially Established, Homogeneously Catalyzed
Reactions
Hydroformylation (Oxo Synthesis/Roelen Reaction)
One of the first major industrial reactions to use homoge-
neous catalysts was the oxo synthesis, which has been exten-
sively investigated. In 1978 the oxo capacity totaled 4.4 million
tons with 2.3 million tons in Western Europe and 1.4 million
tons in North America. This process converts olefins in the
presence of cobalt hydridocarbonyl, carbon monoxide, and
water to aldehydes. Generally the cobalt catalysts are pro-
duced in situ from cobalt compounds and synthesis gas. The
synthesis procceeds at approximately 140° to 180°C and with
a pressure of 200-300 atm. As illustrated in Figure 1, the active
catalyst I reacts with the olefin to form the it complex II which
then yields the alkyl complex III. Following coordination and
insertion of CO, compound IV and the acyl complex V result.
Then, upon addition of hydrogen, the aldehyde is formed and
releases the active catalyst I.
The technical importance of this reaction derives from the
ease with which the primary oxo product, the aldehyde, can
be converted into a multitude of industrially important sec-
ondary products like alcohols, acids, diols, amines, or es-
ters.
Propylene is used primarily as the olefin. The resulting
n-butyraldehyde can be transformed either to n butanol via

Table 1. Comparison oi Homogeneous and Heterogeneous

Table 2. Separation ol Catalysts
Catalysts
Heterogeneous catalyst
Catalyst solid support
Homogeneous catalyst suspension
Homogeneous Heterogeneous
Separation filtration after chemical filtration no problems
Effectiveness
decomposition
Active centers all metal atoms surface atoms only distillation
Concentration small high extraction
Diffusion problems not present present Additional yes small
apparatus
Reproducibility ot catalyst preparation expenditure
Structure known unknown Catalyst return possible easily nol required
Stoichiometry known unknown possible
Modification possibility high small Cost for catalyst high small small
Reaction conditions mild severe loss
Catalyst separation in part costly easy Catalyst concent, small high
Applications limited wide in the product

Volume 61 Number 11 November 1984 961

hydrogenation or, following aldol condensation and hydro-
genation, to 2-ethylhexanol, the most important alcohol for
plasticizers. Starting with higher olefins, one obtained alcohols
and acids which are converted further to detergents, lubri-
cating oils, plasticizers, and solvents. The largest oxo plants
are operated by companies such as BASF, ICI, Kuhlmann,
Mitsubishi, Ruhrchemie, Shell, and UCC.
CHoCHj
aldol I
products by distillation. To do this, the following disadvan-
tages have to be accepted.
Despite higher temperature (180°C), the reaction rate is slower by
a factor of 5 as compared with unmodified cobaltcarbonyl and re-
quires, therefore, a 5-10 times larger reaction volume with corre-
spondingly higher investment costs.
The higher reducing activity of the catalyst results in a loss of
10-15% of the starting olefin; reaction products are predominantly
alcohols.

2CH3CH2CH,CHO - CH,CH2CH2CH=C—CHO Reppe Reactions

condensation
butyraldehyde According to Reppe, a base HX with a mobile hydrogen can
ch2ch3 be added to an olefinic or acetylenic C—C bond with simul-
hydrogenation
taneous insertion of CO (Fig. 2). The insertion of CO is also
-- ch3ch2ch2ch,chch2oh possible on an activated carbon atom, e.g., in alcohols.
2 ethythexanol
Table 3. Catalyst Separation and Return for Different
Using the cobalt catalyst system as a basis, Table 3 shows Oxoprocesses
the steps, such as catalyst separation and return, in the dif-
ferent variations of the technically decisive processes. The Process Separation Method Returned as
catalytieally active cobalt thydridocarbonyl is generally de- Ruhrchemie8 thermal decomposition solid cobalt compounds
composed thermally or chemically. In the Ruhrchemie pro- BASF8 chemical decomposition cobalt acetate solution
cess, for example, the solid cobalt-containing phase that is (CFfeCOOH + Oz)
formed is separated mechanically and returned to the reac- Mitsubishi8 chemical decomposition oil-soluble cobalt soaps
tion. In the BASF process the cobalt carbonyl is first oxidized (carboxylic acid)
and then returned as an aqueous cobalt acetate solution. Kuhlmann 8 extraction under pressure FICo(CO)4 (after release
Depending upon the starting olefin and desired reaction (10 atm) with dilute with HjS04) in the inser-
NaFIC03 solution tion olefin
product, every process has its own specific advantages. In UCC8 chemical decomposition Co(OH)j (after precipitation
contrast to other processes, Shell utilizes hydridocarbonyl- with base)
(HsS04,CH3C00H)
trialkylphosphine catalyst, HCofCOiaFRi. Due to the high Shell® distillation distillation residue
thermal stability of the catalyst, it is possible to separate the
8
HCo(CO)4
®
HCo(CO)3(PR3|
R—CH=CH2
Cobalt- C0/H2 Cat./CO
compound HC=CH + H® -
H—CH=CH-CO®
ch3 Cat./CO
H2C=CH2 + H® -

H—CH2—CH2—CO®
R—CH2—CH2—CHO + R—CH—CHO Cat./CO
straight-chain branched-chain h3c® -> H3C—CO®
aldehyde aldehyde
Co2(CO)g
Catalyst: HCo(CO)4 ®= —OH
Ni(CO)4 —O—Alkyl
H2 Fe(CO)5 —O—Acyl
—NR2 etc.
HCo(CO)4 Figure 2. Elementary Reppe transformation

Ni(CO)4 + HX

v-»- 2 CO

RCH2CH2Co(CO)4 RCH2CH2Co(CO)3

CO X =
Halogen

Figure 1. Mechanism of the hydroformylation with cobalt catalysts. Figure 3. Mechanism of the Reppe acrylic acid synthesis.

962 Journal of Chemical Education

Table 4. Capacities of the Reppe Carbonylation Process (1976) Hoechst-Wacker Process
Insertion Capacity (in Soluble metal-complex salts are the catalysts for the oxi-
agent Product Process tons/year) dation of ethylene to acetaldehyde. As shown in Figure 5, the
Acetylene acrylate and BASF (W. Germany 132,000
acrylic acid and U.S.A.); 30,000
Rohm and Haas (U.S.A.); 140,000 CH CHj
Toagasei Chem. Ind. Co. 36,000
1. h2so4co
Ethylene propionic acid BASF 40,000 H,C=C HSC—C—COOR
2. ROH
Propylene butanol Japan Butanol Co. Ltd. 30,000 I
(BASF—license) ch3 CH3
Methanol acetic acid BASF 40,000 isobutylene Pivalic acid
Borden Chemicals (U S.A.) 52,000 (or ester)
(BASF—license)
R -H or Alkyl

Figure 3 shows the mechanism of the acrylic acid synthesis

from acetylene, carbon monoxide, and water with activated
nickel carbonyl catalyst. The active catalyst [HNi(CO):iX]
adds to the triple bond of the acetylene, and the CO is inserted
in the formed Ni-alkyl bond. The complex thus formed is
subsequently decomposed by alcohol (or water) to yield ester
(or acid) and the active catalyst.
Table 4 shows the capacities of the Reppe carbonylation
installations. The major producer is BASF, which produces
acrylate from acetylene and alcohol, propionic acid from
ethylene and water, and acetic acid from methanol. Although
the Reppe synthesis involves a greater quantity of starting
reagents and reaction products and although it has progresed
in development, the capacities, compared with the basic BASF
technique, have been smaller than those of the oxo synthesis
for the following reasons
The starting agent acetylene is difficult to handle; the transport
especially is problematic.
The Reppe process must compete with other processes that utilize
ethylene and that are often less costly.
Lewis Acid Catalyzed Transformations
The simplest homogeneous catalyst is the proton. Lewis
acid (H2S04, BF3, H3P04) catalyzed processes are employed
industrially to a large extent in alkylation reactions, e.g., in
the production of alkylated gasoline from isobutylene as well
as of cumene, xylene, and styrene from benzene.
PdCVCuCfe/HC!
CH2=CH2 + 1/2 02- CH3CHO

[PdCh]2-

cumene styrene

A variation of a CO-insertion known as the Koch synthesis is

shown in Figure 4, Olefins or other compounds that in the
presence of acid catalyst readily convert to carbocations react
with carbon monoxide and water to produce carboxylic acid
or with alcohol to yield the corresponding ester. The starting
reagent (olefin, alcohol, or aldehyde) reacts thereby with a
proton to form a carbocation VI which then adds CO. The
generated acylium ion VII, after addition of alcohol, forms the H+
oxonium complex VIII. This complex decomposes into the
desired carboxylic acid or into the corresponding ester
whereby the active catalyst is again freed.
The most important starting olefins are isobutylene and
diisobutylene as well as mixtures of olefins in the range of Cg
to C10 (from oil). The highly branched carboxylic acids formed
(e.g., pivalic acid) are starting materials for resins, lacquers,
and synthetic lubricating oils. The reaction conditions are
relatively mild (pressures up to 70 atm and temperatures to
a maximum of 70°C); however, expensive and corrosion-re-
sisting material must be saved. Main producers are Shell,
Enjay Chemical Co., and DuPont. The total world production Figure 5. Ethylene transformation using palladium catalysts (Wacker pro-
is estimated to be ~150,000 tons per year. cess).

Volume 61 Number 11 November 1984 963

 n (CH2=CH2)-
AKCjHnli
H2C=CH—(CH2—CHz)„ -CH2—CH3
reaction forms 7r-complex IX, the coordination complex of
ethylene and palladium(II), and upon nucleophilic attack by
water converts to X. It is still unclear as to how the hydrox-
ylated ethyl group in compound X converts to acetaldehyde
and how the complex breaks down, A reasonable path is the
transfer of hydrogen from the /3-carbon atom in X to palla-
dium with the formation of the vinylalcohol complex XI. The
palladium(O) is continually regenerated to PdCl2 in situ by
the redox system Cu(I)Cl/Cu(II)Cl2, HC1, and oxygen. The
reaction conditions are mild (e.g., the two-step Wacker process
operates at 10.5 atm and 125° to 130°C). The process can be
carried out either in two steps with air or in one step with
oxygen. The yield in both cases is approximately 95%, The
application of these two variations is determined more by
factors such as cost of oxygen than by major differences. This
process, known only since 1960, had by 1979 reached a pro-
duction of approximately 2.24 million tons per year.
Oligomerization of Olefins and Dienes
Olefins and dienes can be oligomerized by means of ho-
mogeneous catalysts under mild conditions. According to the
Figure 7. Mechanism of the cyclo-oligomerization of butadiene (a) to cyclodeca-1,5,9-triene using a nickel(0)-7r-bisallyl catalyst, (b) to 1,5-cyclooctadiene (when
L is of low basicity) or 4-vinylcyclohexene (when L is strongly basic) using nickel(0)-7r-bisallyl- or nickel(0)-5r-(r-bi$allyl catalysts, respectively.
964 Journal of Chemical Education
Aifen synthesis (Ziegler) (see Fig. 6), the catalyst triethyl-
aluminum, A1(C2H5)3, reacts with ethylene in a so-called
Aufbau reaction by insertion of the ethylene into the alumi-
num-carbon bond. The aluminum complex thus formed can
accept additional ethylene molecules until finally the growing
alkyl chain is set free as an a-olefin and the tri-alkylaluminum
is regenerated. The Aufbau reaction and displacement reac-
tion are favored by low temperature and high pressure (90-
120°C and 100 atm) and high temperatures and low pressure
(200-300°C and 50 atm), respectively.
The isomer formation, besides being dependent on the re-
action conditions, can be highly influenced by the ligands on
the aluminum. This is generally true for all homogeneous
catalysts. An impressive example is the oligomerization of
dienes according to Wilke.
Active catalysts for such reactions are nickel(0) complexes
with little steric hinderance (no ligands) such as represented
by the bis-7r-allyl compound XII (Fig. 7a). This compound can
accept an additional butadiene molecule with the subsequent
formation of XIII. Further addition of butadiene leads to
cyclododeca-l,5,9-triene and the free nickel catalyst.
When one of the coordination sites on nickel is blocked by
a ligand (L) as in XIV (Fig. 7b), the result is almost entire
formation of eight-carbon compounds. A highly basic ligand
converts XIV to XV since the central atom in XV can better
accommodate the extra electrons of the ligands L. In the dis-
placement reaction with new butadiene, XIV reacts to form
1,5-cyclooctadiene while XV leads to 4-vinylcycIohexene.
The long-chain a-olefins are important starting reagents
for the production of lubricating materials, plasticizers, de-
tergents, and polyamides.
Of special importance are mixed catalyst systems since a
higher degree of selectivity can be achieved with these. Pro-
cesses of industrial significance for the ethylene oligomeri-
zation are the Esso process with alkylaluminum chloride and
titanium tetrachloride, the Shell process with nickel-phos-
phine catalysts, and the Ethyl process with the classical Ziegler
tri alkylaluminum catalyst. In 1975 Hiils began the production
of cyclododecatriene from butadiene with a titanium-tetra-
chloride/diethylaluminum chloride catalyst.
Total capacity of the oligomerization process is about
800,000 tons per year of which approximately 90% consists of
the a-olefins.
Homogeneous Oxidation Reactions in the Liquid Phase
Of great importance also is the oxidation of various sub-
stances by homogeneous catalysts, for example cyclohexane
to adipic acid (USA, 1977; 700,000 tons), butane to vinegar
(USA, 1977; 986,000 tons), propylene to propylene oxide and
especially p-xylene to terephthalic acid (USA, 1977; 2.277
million tons). The assumption for example is that in the oxi-
dation of p-xylene, the intermediate hydroperoxide converts
the Co2+ and Mn2+ ions to 3+ ions which then abstract a
benzylic hydrogen atom inducing further oxidation.
CH, CH, COOH
p-xylene terephthalic acid
These ions also aid in the decomposition of the intermediate
hydroperoxides. It is still not clear if the metal ions also play
a role in the activation of oxygen through complex formation.
With xylene as the starting agent the major products are
terephthalic acid and dimethyl terephthalate. For the tech-
nical production different processes were developed by
Amoco, Toray, and Dynamit Nobel.
Hydrocyanation (DuPont)
The direct addition of hydrocyanic acid to butadiene can
be accomplished with nickel(0) phosphine or phosphite
complexes at standard pressure and 30-150° C in oxygen-
containing solvents such as tetrahydrofuran. A plant pro-
ducing 100,000 tons/yr has been in operation in Texas since
1977. Additional plants are being built.
CO + H2 —
CH3OH co CH3C02H
synthesis gas
Compared with the older BASF process, which was likewise
homogeneously catalyzed and marked by high reaction tem-
peratures of ~250° and by pressures around 750 atm, the
Monsanto process operates under considerably milder reac-
tion conditions. Applied to methanol, a selectivity of 99% is
achieved and with the cobalt process, 90%. Because of the high
price of rhodium, a complete recovery of the catalyst is abso-
lutely essential if the process is to be economically efficient.
A similar example for pressure reduction is the rhodium-
catalyzed UCC-oxo-process. Triphenylphosphine, PjCeHjla,
is used as co-catalyst. The mechanism is largely like the known
oxo process which utilizes the hydridocobaltcarbonyl
catalyst.
The advantages of the rhodium process compared with the
classical cobalt process are
reduced pressure (10-25 atm)
better proportion of normal to isoaldehyde in the final product
(90:10 as opposed to 30:20).
On the other hand, the cobalt process distinguishes itself
by
greater flexibility with regard to starting olefins (C2 to C2o) and
reaction products (aldehydes, alcohols),
the possibility of improved energy recovery since high temperatures
are used.
Critical evaluation of the efficiencies of both variations from
all viewpoints holds them to be about equal.

H Future Developments in Homogeneous Catalysis

NC. /CH, /CH, Further development in homogeneous catalysis will center
+ 2HCN XH, CH, CN
around the following
adiponitrile
H
1,3-butadiene
variation of the central atoms,
introduction of new ligands,
Newer Industrial Developments variation in the application phase, and
new chemical reactions.
Besides the established processes summarized above, there
exist new developments which only recently have been in-
troduced into major production. With Wilkinson’s metal
complex tris(triphenylphosphine)rhodium chloride, [Rh(diene)L2]
+
ClRh[P(C6H5)3]3, it is possible to selectively hydrogenate
biologically active substrates like steroids. The value of this H2-^ Diene
catalyst is based upon the fact that the hydrogen is transferred
specifically to the cis positions. [RhH2L2]+
Figure 8 shows a typial course of a reaction of a homoge-
neously catalyzed hydrogenation. Monsanto, for example
using this reaction, converts cinnamic acid derivative XVI by
asymmetric hydrogenation into the levo-rotating precursor
of L-dopa (3,4-dihydroxyphenylalanine), L-dopa is formed
after cleavage of the acetyl protecting group from nitrogen.

3,4-dihydroxyphenylalanine
L-aopa

As a drug, L-dopa is effective against Parkinson’s disease.

Monsanto’s rhodium-catalyzed acetic acid process is an
example of the effort to replace the conventional high pressure
processes with low pressure ones and to substitute coal for oil
in the production of basic chemicals. Methanol, the starting
agent for the synthesis as well as CO from synthesis gas can Figure 8. Reaction mechanism of a homogeneously catalyzed reduction of
be produced from coal. olefins with a rhodium catalyst.

Volume 61 Number 11 November 1984 965

Variation of the Central Atoms
It is known that certain transition metals are especially
suitable for specific reactions. For example, under hydro-
formylation conditions styrene with cobalt carbonyl catalysts
is almost exclusively hydrogenated, whereas with the rhodium
catalyst the reaction leads almost quantitatively to hydro-
formylation. It is generally recognized that cobalt has a greater
tendency to hydrogenation than rhodium. It seems that cobalt,
as a hard metal in the sense of the theory of hard and soft
bases, eases the oxidation addition of the hard water in the key
step of the reaction. Correspondingly, the initially formed
aldehydes are partially reduced to alcohols by cobalt but not
so by rhodium. Cobalt and nickel catalysts are quite advan-
tageous in the oligomerization of conjugated diolefins, whereas
titanium, vanadium, and chromium catalysts are more suit-
able for a-olefins. Variation of the central atom permits a
coarse adjustment of the selectivity of the homogeneously
catalyzed process, while the fine tuning can be achieved
through modification of the ligands as well as the reaction
conditions.
New Ligands
Ligands on the transition metal catalyst influence the
electronic and steric structure and thereby facilitate a derived
steering of homogenously catalyzed process. In the future,
through ligand modification, the selectivity of many processes
will be further unproved. A prime example of the desired
modification of ligands is the development of the stereose-
lective catalysts for asymmetric hydrogenation, where the
basic principles of “catalyst tailoring” are clearly evident. A
planned variation of the ligands of the rhodium complex led
finally to the ligands “dipamp.”
OCH, OCH,
“Dipamp:” 1,2-bis-phenyl-anisylphosphineethane
Rhodium complexes with this ligand are capable of hydro-
genating amino acid precursors to optically active amino acid
with up to 95% optical purity (This corresponds to an enan-
tiomeric ratio of 98:2). The Monsanto amino acid process
makes use of this in the production of L-dopa.
Variation in the Application Phase
At present the major areas of investigation are
lowing
the immobilization of homogeneous catalysts,
the catalyst on metal clusters,
the multiphase catalysis, and
the development of newer chemical reactions.
As in the peptide synthesis, the attempt in the immobili-
zation is to fix the active, homogeneous combination of the
central atom and ligands onto a heterogeneous matrix. An
example is shown in Figure 9. In general, the union of the ac-
tive homogeneous combination of central atom and ligands
to the matrix is achieved via coordinate or covalent bonding.
The basic problem of this catalyst type lies in the divergence
between the required high stability of the fixed catalyst and
the required lability of the ligand sphere around the central
atom for catalytic activity. Thus, a relatively stable catalyst
with minimal activity exists or there is the reverse, an active
catalyst with concomitant loss of metal through elution.
Variants of the immobilized catalysts are the metal cluster
catalysts. By joining several single nuclear complexes to
multinuclear clusters via metal-metal bonds, an insoluble
heterogeneous catalyst finally forms. This is also of interest
scientifically, in that the surface of the clusters, in principle,
966 Journal of Chemical Education
corresponds to the surface of a heterogeneous metal catalyst
and, as such, is the basis for the hypothesis that the catalytic
behavior of these two should be the same.
In the multiphase catalysis, the catalyst is dissolved in a
solvent in which the substrate is insoluble. An example of this
technique is the above-mentioned successful oligomerization
process. In this Shell AG process the ethylene passes in bead
form through a diol phase which contains the nickel catalyst
(Fig. 10) and is there oligomerized to higher a-olefins; these
leave the catalyst phase without going into solution. The
product and catalyst solution is thus easily separated through
simple phase separation. Similar processes have been devel-
oped for hydration and hydroformylation.
In the broadest sense the application of fused salts belongs
to multiphase catalysis. These can serve as reaction media or
as catalytically active species. The special properties of such
melts offer certain advantages
high chemical stability (make high temperature reactions
easier),
lower vapor pressure (eases high temperature reactions),
good thermal and electrolytic conductivity, and
dissolving capacity for oxides, hydrides, metals, and carbides.
Corrosion causes a technical problem, which is intensified
additionally by the relatively high temperatures (400-700°C).
A few examples of applications of salt melts to catalytic re-
actions are the chlorination of methane to a mixture of chlo-
rinated methanes (CuC^/KCl melt), the chlorination of eth-
ane to vinyl chloride (CuO/CuC12/KC1), the selective hydra-
tion of polyenes (PtCl2/(C2H5)2NSnCl4), hydration of coal
(ZnCL/KCl), and the production of monosilane, SiH4(LiCl/
KC1).
The transformation of synthesis gas is a focus in the search
for new reactions that could be homogeneously catalyzed. It
the fol-
- Rh(CO)2
L
D =
Donor Atom (P, As, N, Sb)
Figure 9. A rhodium complex coordinate covalently bonded to a solid support
of polystyrene-divinylbenzene copolymer.
rcCH2=CH2
l^ss dense
CH3CH2 + CH2CH2 + nCH=CH2 Phase
75-120°
Catalyst solution more dense
53 bar
phase
Nickel salts
Solvent: Diol
NaBH„
Figure 10. Oligomerization of ethylene in a two-phase catalysis.
 that new scientific knowledge could accelerate
is in this area For the hydrogenation of coal a ZuC12/KC1 melt is used; in the
the substitution of coal for petroleum Fischer-Tropsch synthesis the catalyst Ir4(CO)i2 is in a
Methane formation NaCl/AlCl3 melt at 180°C and 2 atm or pressure. A decisive
breakthrough, however, will be possible only when newer, very
CO + 3 H2 -
CH4 + H20 noncorrosive materials are developed. In the synthesis of
homologous alcohols the synthesis gas can serve as the starting
Glycol synthesis base for methanol, ethanol, and higher alcohols.
2 CO + 3 H2 —
HOCH2CH2OH
Outlook
Hydration of coal Homogeneous catalysis has, within a few years, captured
C + H2 —»
-fCH2-)-
an important part of the technically applied processes in
chemistry. Additional processes that could be industrially
Fischer-Tropsch synthesis utilized include: the introduction of new catalysts with new
ligands, the discovery of new reactions (for example the acti-
CO + 2 H2 —
GCH24 + HaO vation of C—C and C—H bonds), the improvement of existing
Formation of homologous alcohols processes, and the variation of the application phase. In the
future energy and raw material considerations will increas-
ROH + CO + 2 H2 —
RCH2OH + H20 ingly determine the direction of world-wide development of
Methanol synthesis traditional industrial organic chemistry. Since homogeneous
catalysts are generally active at low temperatures, new de-
CO + 2 H2 —
CH3OH velopments can be expected in this area. Great advances will
Osmium and iridium carbonyls should be catalytically ac- occur where processes based on petroleum can be replaced by
tive in the methane formation. A homogeneous titanium synthesis gas technology based on coal or where carbon
complex reacts stoichiometrically under mild conditions. In dioxide as the end product in the hydrocarbon cycle can be
the glycol synthesis (important quantity-wise) the discovery recycled as a starting agent.
of a rhodium carbonyl cluster catalyst that is active with Of special interest in the long term are the homogeneously
synthesis gas could open the possibility of replacing the eth- catalyzed processed based on water and air in which the re-
ylene with synthesis gas as the raw material. quried energy could be supplied by the sun, an ever-available
energy source. Examples of such applications exist: the re-
2 CO + H2 Rh12(CQ3)4 t HOCH2CH2OH duction of atmospheric nitrogen to hydrazine, the activation
synthesis gas 2io-2.w°c glycol
of oxygen for fuel cells, and the photochemical splitting of
water into hydrogen and oxygen. In these processes the car-
For the Fischer-Tropsch synthesis as well as for the hy- bonyl catalysts as well as the cluster compounds could make
drogenation of coal, a salt-melt variation has been developed. a decisive contribution.

A Useful Model for the “Lock and Key” Analogy

One of the most generally useful analogies for the specificity of enzymes
toward substrates is the well-known “lock and key” hypothesis1 originally in-
troduced by Emil Fischer in 1894. A useful model that nicely illustrates this
principle is the “SOMA" puzzle cube2 (see figure). By using differently colored
sets it is possible to arrange them as in the figure. Manipulations quickly dem-
onstrate that the “enzyme” cavity will only be filled with one of the two similarly
shaped “substrates.” This demonstration can be extended to include an analogy
concerning the differences in physiological properties possessed by many en-
antiomeric pairs (e.g., flavor-enhancing properties of MSG, (monosodium glu-
tamate) versus its enantiomer). As can be quickly seen, the two “substrates”
are indeed enantiomeric and only one will completely fill the “enzyme” cavity.
The demonstration is made clear to a small class by using the models in the front
of the class. By using either single 35-mm slides or lap-dissolve projection,3 the
concepts can easily be conveyed to any size class.
Another use of this relationship can be made concerning the odor differ-
ences that exist between R and S carvone.3 This clearly emphasizes the con-
troversy concerning the stereochemical versus the other theories of odor rec-
ognition.

1
Jencks, W. P., “Catalysis in Chemistry and Enzymology," McGraw-Hill Book Company, New York, 1969, p. 288.
2
“SOMA” by Parker Brothers, Inc., P.O. Box 900, Salem, MA„ 01970.
3
Harpp, D. N. and Snyder, J. P., J. Chem. Educ., 54, 68 (1977); Fine, L. W., Harpp, D. N,, Krakower, E., and Snyder, J. P., J. Chem. Educ.,
54, 72 (1977).
*
Russell, G. F. and Hills, J. I„ Science, 172, 1043 (1971); Friedman, L. and Miller, J. G„ Science, 172, 1045 (1971).

Ariel E. Fenster David N. Harpp Joseph A. Schwarcz

John Abbott College McGill University Vanier College
St. Anne de Bellvue, Que., Canada Montreal, Que., H3A 2K6 Canada Montreal, Que., H3X 2N9 Canada

Volume 61 Number 11 November 1984 967