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Contents
Abstracts 68
New Patents 75
In a truly heroic effort the National Cancer now known concerning the activities of these
Institute of the U.S. Government has compounds. It will be taken as granted that
screened approximately 140,000 compounds the general reader of this journal will find, as
for anti-cancer activity over the past 15 years. did the author, that biological and medical
Of this number, however, only a dozen or so terminology are "terra incognita". T o offset
were inorganic compounds. This imbalance this to some extent, a glossary of the more
between organic and inorganic compounds important terms is appended to the article.
reflects a fashion in chemotherapy that The germinal discovery was made about
started over 35 years ago. Prior to that, heavy 1964 when platinum electrodes were used
metals were extensively used in medical to apply an alternating electric field across a
therapy. About 1935, the discovery of the chamber in which bacteria were growing ( I ) .
sulfonamides introduced a new class of Application of the electric field caused a
organic chemicals which were effective cessation of all division in the E. coli rods,
against many bacterial infections. Hard on and since growth was not inhibited, resulted
this came the development of the antibiotics in the appearance of long filaments, A
which coupled a high degree of efficiency with comparison of the normal appearing E. coli
a low toxicity. At present, excepting a few rods and the filamentous rods caused by the
outstanding drugs, heavy metals and other application of the electric field are shown
inorganic chemicals have ceased to be of under the same magnification in Pig. I.
active interest as chemotherapeutic agents. Extensive detective work was required before
The screening program of the National we could conclude that the effective agent in
Cancer Institute, occurring within the last blocking cell division in the bacteria was a
15 years, reflects this bias. small concentration (-10 ppm) of some
Recently a new class of potent anti-tumour platinum complex in solution, electrolytically
agents has been discovered. These are formed by the applied electric field. It re-
inorganic complexes of the transition metal quired much further work to determine that
Group VIIIb. I n this article we shall review these complexes were cis-dichlorodiammine-
briefly the history of this new development platinum(I1) and cis-tetrachlorodiammine-
and discuss some of the properties that are platinum(1V) (2,3).
The structures of these complexes and some chloroplatinum(I1) double negative ions are
other differently acting agents are shown in bacteriocides at low concentrations (I to 6
Figs 2, 3 and 4. With the verification that ppm in the bacterial growth medium). These
these platinum complexes were indeed compounds undergo photochemical changes
capable of selectively blocking cell division in in the bacterial media, leading to a subse-
bacteria, a series of investigations was under- quent replacement of first one and then a
taken to determine the mechanism and the second chloride by ammonia. The resulting
generality of the effect. VanCamp discovered neutral molecules arc not bacteriocides until
that the hexachloroplatinum(1V) and tetra- very high concentrations ( - IOO ppm in
solution) are reached. Interestingly, the E. coli have previously been infected by
trans forms of these neutral molecules are not viruses (bacteriophages) and that the genetic
effective in blocking cell division in bacteria, material of the virus was incorporated into
while the cis isomers are. Thus we have two and became part of the genetic material of the
groups of compounds with different bacterial bacterial cell. T h e viral genetic material
effects; the negative ionic species which are (genome) is repressed in these cells and is not
generally bacteriocidal, and the neutral normally detectable. Such bacterial strains
species, in the cis form, which block cell are called “lysogenic” for the simple reason
division, but not growth. Gillard and his co- that a number of agents, such as ultraviolet
workers have reported similar effects in light, X-rays, and some chemicals such as the
organic rhodium complexes (4), and Gale, nitrogen mustards (alkylating agents), are
Howle and Smith (5) have extended these capable of inducing the development of partial
observations to include photochemical re- or complete viruses which lead finally to the
actions in ammonium hexachloroiridate, destruction (lysis) of the cell. The platinum
which also parallel the platinum trans- compounds which are effective anti-tumour
formations and bacterial activities. agents were found to be extremely potent
A third class of bacterial effects of platinum in inducing lysis of such lysogenic bacteria.
compounds was discovered much later by Fig. 5 exhibits the three types of effects on
Keslova (6). It is known that some strains of the growth curves in test tubes of various
oxalatoethylene- tris(cthy1enediamine)-
diamineplatinum( 11) platinum(I1) ion
b‘ig. 4 Strurturcd formulae of high toxicity, non-active complexes ofplatinum
By J. E. Philpott
Johnson Matthey Metals Limited
The rare occurrence of inactive catalyst gauzes for no obvious reason has
led to comparative studies of the structures of rhodium-platinum wires
from both active and inactive gauzes. Active gauzes showed the regular
development of octagonal crystal faces on the nodular growths on the
wires. Inactive gauzes showed no crystal development and an amorphous
growth appeared on the wires. Segregation of rhodium and iron at the
surface occurred in this case, perhaps due to unusual plant operating
conditions, and may have caused deactivation.
The use of rhodium-platinum alloy gauze and uneconomical yields are obtained only a
as the catalyst in the modern process for short time after igniting the pad. It would
ammonia oxidation is well established, as appear that the high selectivity of the catalyst
shown by the large number of papers re- gauzes for promoting the desired oxidation
viewed previously in this journal ( I ) and reaction steadily declines and that yields from
elsewhere (2). At the present time there are alternative side reactions become significant.
in the world more than 450 nitric acid plants Treating the inactive gauzes with constant
and almost without exception they use plati- boiling hydrochloric acid and replacing them
num alloy catalyst gauzes, usually of 10 in the plant does not improve their per-
per cent rhodium-platinum. formance. Replacement of the inactive pad
T h e oxidation process is highly efficient by a fresh pad of gauzes has always overcome
and over a wide range of operating conditions the problem but has done nothing to explain
a nearly quantitative conversion of ammonia it.
to nitric oxide can be obtained. Conversion Analytical examinations of inactive gauzes
efficiencies of between 92 and 96 per cent are and of the material from which they were
commonplace and are consistently achieved woven and cut do not give any indication of
throughout the lifetime of a plant. I n general the cause of inactivity. The chemical
the shortfall from maximum efficiency is composition of the gauze material has always
probably due to some decomposition of the been found to lie within the tolerance limits.
ammonia feedstock before it reaches the Analysis to determine whether some unusual
gauzes, rather than to significant yields from impurity had been sealed into the wire
possible alternative reactions ( I , 2) that can surface during the wire drawing process, or
take place on the gauzes. whether the retention by the gauzes of
On rare occasions, however, a case is found impurities entrained in the feedstock gas
of a catalyst gauze pad that is inactive. might account for the drop in activity, did
Although apparently indistinguishable from not reveal any cause of the inactivity.
other gauzc pads, the inactive gauze pad does Although inactive gauze pads occur in-
not maintain its initial conversion efficiency frequently and are more of an occasional
embarrassment than a constant cause of It has been previously reported (3) that
trouble, a niore detailed examination of them rhodium-platinum gauzes develop nodules or
was undertaken as part of a research pro- “brussels sprout” growths on their surfaces
gramme to study the fundamental mech- while in operation in nitric acid plants. The
anisms involved in ammonia oxidation for catalytic activity of the gauzes appears to
nitric acid production. be related to the development of this nodular
growth, since fresh gauzes with smooth as-
Examination of Inactive Ganzes drawn wire surfaces are inactive and need to
’To this end a number of inactive gauzes be activated before they will oxidise ammonia
from two medium pressure plants were efficiently. For this reason replacement
examined at various periods in their lifetime gauzes are usually installed beneath some of
and the results, together with the results the older activated gauzes already in the
from a more general examination made of catalyst pad. When a new pad is being
spcnt gauze pads taken from all types of commissioned, each gauze in the new pad is
plant in various parts of the world, were activated by playing a hydrogen flame over
compared with those obtained from an its surface until the gauze just glows red.
examination of several inactive gauzes from Alternatively, a few activated gauzes obtained
two inactive gauze pads. A description of the from a plant already in commission are
results follows with a series of scanning inserted on top of the fresh gauze pad and
electron microscope and electron microprobe serve to ignite the remainder.
analyser photographs illustrating the state of The photograph in Fig. 2 shows a gauze
the gauze surface at various stages. of 0.003 inch diameter wire with the wire in
Fig. 7 (right) Electron and X-ray images of spent active gauze showing its homogeneity. n (top) l<lectron
imugge of rross-section of gnitse. b (middle) Pt M u X-ray image. c (bottom) K h 1,cr X-ruy image. x 360
‘The development of
these inactive surfaces is
the subject of further
research work and in a
later article it is hoped
that an explanation will be
given of the fundamental
causes that lie behind these
observations.
Acknowledgements References
The author is much indebted to Dr G. J. I<. I H. Connor, Z’latinum Metals Rev., 1967, 11,
Acrcs for helpful discussions and to Mr J. G. (I), 2-9 Ibid.; (2), 60-69
l h y , who obtained the scanning electron micro- 2 T. E L Chilton, Chem. Engng. Prog. Mon. Ser. 3
scope and electron microprobe analyser photo- 3 A. W. Holmes, Platinum Metals Rev., 1959, 3,
graphs. ( I ) , 2-8
While conducting research here at the Three crucibles were electroformed. One
Metallurgy Research Center on thc elec- is of iridium, one inch inside diameter and
trodeposition of platinum group metals from $ inch deep with a 5 mil wall. The second
molten cyanide baths we have prepared crucible is formed of platinum, 2 inch inside
platinum metal objects by electroplating or diameter and one inch deep with a 5 mil
electroforming. The electrodeposition of wall. The third, also of platinum, is electro-
platinum group metals on various substrates formed with a thermocouple well for differen-
from molten cyanide baths was described tial thermal analysis work, inch inside
by Rhoda ( I ) . We have described our diameter, 2 inch deep with a 15 mil wall.
modified methods to electrodeposit thick Crucible tongs were coated with platinum,
protective coatings of platinum, iridium (2), 2.5 mil thick on the arms and 5 mil thick on
palladium (3), and rhodium (4)from molten the tips. I n addition, such items as thermo-
cyanides. couples, a nickel-chromium-iron rod used
,
I hree c:rucibles urtd two pairs of crucilrles tongs fdwictited und coated with platinum metals.
I
T h e largcst crurible was electrofornied of iridium, the others of platinum. The tongs it1er~
couted with plntinum. Wall and coating thicknesses range ,from 2.5 mil to 15 mil.
A thermal e.m.f. is not only a function of Extrapolation of the results obtained shows
temperature, it is also affected by pressure, that Chromel: Alumel may read as much as
a fact that is not as widely known. T o the z8'C high at IZOO'Cand 50 kbars while
geophysicist studying chemical and physical platinum : 10 per cent rhodium-platinum
behaviour at pressures of several thousand reads low by a similar amount at zooo"C
atmospheres correction for the effect of and 50 kbars.
pressure is essential. T h e authors acknowledge that pressure is
I n a recently published paper I. C. Getting only one of several factors affecting the e.m.f.
and G. C. Kennedy (I) describe a technique generated by a thermocouple and observe
for determining corrections on single thermo- that chemical contamination is a particularly
elements where, under thermally symmetrical difficult problem. Unfortunately their paper
conditions, one-half of a homogeneous wire does not indicate whether any steps were
is pressurised while the other half is main- taken to measure the degree of contamination
tained at atmospheric pressure. This is a and if so how their results were adjusted to
method previously used by Wagner (2), allow for this factor. Curiously they also omit
Hridgman (3) and Bundy (4) among others. an expIanation of the value of extrapolating
Getting and Kennedy's apparatus con- to 2000 C when the platinum limb of a
sisted of a piston-cylinder device with talc thermocouple normally melts at 1772'c.
as a solid pressure medium. T h e thermocouple The reader is left to infer that pressure
wire was fed through a tube at atmospheric raises the melting point sufficiently to make
pressure to the thermal centre of the furnace this a meaningful exercise.
where it entered the cell through a pressure These criticisms apart the results should
seal. Inside the cell the wire was coated prove to be valuable to workers in this
with binderless boron nitride to preserve experimentally exacting field of research
electrical insulation yet ensure uniform where reliable data on e.m.f. correction are
pressure transmission. T h e temperature of still very scarce.
both seals was recorded so that the temperature P. H. W.
gradient along which the pressure was
applied could be calculated. The cell was References
heated internally by a co-axial graphite heater. I I. <;. Getting and G. C. Kennedy, J . Appl.
A number of excursions were made into PhYS.9 1970, 41, (II), 4552-4562
the pressure-temperature field ranging up 2 E. Wagner, Ann. Phys., 1908,27,955
to a maximum of 1o0o"C and 35 kbars. T h e 3 1'. W. Bridgman, Proc. Amer. Acad. Arts Sci.,
thermocouples selected were Chromel :Alumel 1918,53,269
and platinum: 10per cent rhodium-platinum 4 I;. P. Hundy, J . Appl. Phys., 1961, 32, (3),
since these are two of the most commonly 483-488
used combinations. These thermocouples 5 1'. M. Bell, I:. R. Boyd and J. L. England,
Carnesie Inst. Wash. Yr. Bk., 1968, 66, 545-547
have previously been the subject of investi- 6 R. €7. Hanneman and H. M. Strong, .7. Appl.
gation by Bell et al. ( 5 ) , and Hanneman and Phys. 1966, 37, (2), 612-614; J . Appl. Phys.,
Strong (6) among others. 1965, 36, ( 2 ) , 523-528
ii Pt
susceptibility to electrophilic attack.
C 5P2
I
flected in the enhancement of the activation
I i’t
of the olefin towards nucleophiles, whereas
highly electronegative substituents on the
olefin (e.g. CF, groups) would cause an
even greater electron movement from the
For such a metal the metal-olefin bond metal to the olefin. Many of the reactions of
obviously depends upon : metal-olefin complexes may be rationalised
(i) T h e metal, its electronic configuration in these simple terms. Other factors, of
and oxidation state; course, must also be considered. Often, for
(ii) the auxiliary ligands present; and example, auxiliary ligands produce strong
(iii) the olefin itself. steric effects which cause modification of the
Consider, for example, Zeise’s salt, an reaction path.
ethylene complex of platinum(I1). Since the
metal is in a relatively high oxidation state Stabilisation of “Unstable” Organic
a drift of electron density away from the Moleeules
ethylene to the metal via the o-bond ((a) Perhaps one of the most dramatic aspects
above) would be expected. For the same of this field is the stabilisation of organic
reason little drift of electron density back to molecules which do not exist in the free
the olefin via the x-bond is expected to state. Beyond question the most notable
occur. Consequently the ethylene acquires example of this type of behaviour is cyclo-
a net 8 character and undergoes nucleo- butadieneiron(tricarbony1). Cyclobutadiene
philic addition reactions. has excited organic and theoretical chemists
the thermal
Related to thedecomposition of x-allyl-pal-
behaviour discussed above is
ladium acetylacetonate (7) to give allylacetone
@
>
.
I
Pd ( = )H/ N
OAa co % CJgg
(8) via ligand coupling.
Other coupling reactions find their uses :
Ph
WP
Ph C E CPh + CO
- JO
(
'CI
- 50- - C_yq
compound may be formed with Fe(O),
Ru(O), Os(O), Rh(I), Ir(I), Pd(I1)
or Pt(I1). As discussed above (commencing In contrast, the analogous complexes of
on page 63) for the formation of carbon- Rh(I), Ir(I), Fe(O), Ru(0) or Os(O), do not
carbon bonds, the complexes of palladium undergo such additions but rather electrophilic
reactions of the type:
L-
O &
J
1 -+ + I?@- RU(CO),
0 . (+I )I
'.__I
a (In)
derivatives. I n the main this facet of this
chemistry is poorly explored. T h e role of
the metal and the auxiliary ligands is obviously
critically important but relatively few sys-
tematic studies have yet been done.
NEW PATENTS
METALS AND ALLOYS E1,ECTRODEPOSITPON AND
Gold-based Spinnerette Alloy SURFACE COATINGS
JOIINSON, MATlIIhY & GO. LTD. Coating or Inlaying
U . S . Patent 3,529,959 JOIINSOS, MATTHEY & CO. LTD.
A gold-based spinnerette alloy contains between British Patent 1,207,970
so':,, and Eo",,, Au, between 0.04 and 0.5';,) I r A C u or Cu alloy is coated or inlaid with a thin
and the remaining part Pt, apart from the layer of a noble metal such as Au, Ag, Pd or Pt
impurities. ,4 method of making the alloy con- or alloys thereof by interposing between the two
sists of induction melting the components, casting a layer of Ni, Ye, Co, Mo, or V, and heating
a sheet and homogenising. the three layers under pressure to bond them.
Reductive Vapour Deposition of Osmium
CIIEMICAL COMPOUNDS EKGLISH ELECTRIC VALVE CO. LTD.
British Patent 1,209,318
Osmium Carbonyl High purity 0 s deposits are obtained on a sur-
JOHNSON, IMATTHEY & CO. LTD. face by vapour deposition from an OsO,/Hz
U .S. Patent 3,508,870 mixture. OsO, is dissolved in water at room
Method of prcparing 0 s carbonyls is described. temperature and H, (or a gas containing H,)
A solution of OsO, in an inert hydrocarbon bubbled through the solution. The resulting gas
solvent is heated to an elevated temperature is mixed with another reducing gas to give a
under super-atmospheric pressure in the presence predetermined ratio of OsO, to reducing gas.
of CO. The product is primarily Os,(CO),, In contact with a hot body this gas deposits
with traces of Os,O,(CO), ,. metallic 0 s .