Pxoceedt*u^ t6e

Pacific Southwest Association of Chemistry Teachers

George B. Kauffman
Fresno State College
Sophus Mads Jorgensen (1837-1914)
Fresno 26, California
A chapter in coordination chemistry history

Today most chemists, regardless of Biography

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their field of specialization, are acquainted with the

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Sophus Mads Jprgensen was born in Slagelse,

nature and importance of the work of Alfred Werner.
Denmark, on July 4, 1837. His early schooling was
Indeed, practically every freshman chemistry student obtained at Slagelse and later at the Sor0 Velvillie.
is now introduced to at least the essentials of his coor-
At this academy, his interest in chemistry was awakened
dination theory. Yet, except for those who have had
occasion to delve into the study of complex compounds,
by F. Johnstrup. This dedicated teacher allowed the
older students to work in his own private laboratory
the name of Sophus Mads Jprgensen remains entirely on Sundays, and Jprgensen eagerly availed himself of
unknown. the opportunity.
Few realize that Werner’s new and revolutionary
After his graduation in 1857, Jprgensen entered the
theory was based upon experimental data carefully and
University at Copenhagen and in 1869 received his
painstakingly accumulated over a number of years by doctorate with the dissertation “Overjodider af Alka-
Sophus Mads Jprgensen, professor of Chemistry at the loiderne’’ (Polyiodides of Alkaloids). In 1871 he
University in Copenhagen (1871-1908). It is perhaps became Lektor at the University and in 1887, Profes-
not an exaggeration to say that Werner’s theory might
sor of Chemistry, a position which he held until 1908,
never have been propounded had not Jprgensen’s work the year of his retirement. He died on April 1, 1914.
provided the observations requiring explanation. During his 41 years of teaching, Jprgensen exerted a
Except for some early isolated research, Jprgensen profound influence on a whole generation of Danish
devoted himself exclusively to investigating the coor-
chemists and may even be said to have founded a
dination compounds of cobalt, chromium, rhodium, school. Such outstanding men as O. T. Christensen,
and platinum, and this work, upon which his fame E. Koefoed, Niels Bjerrum, and S. P. L. Sprensen
rests, forms an interconnected and continuous chain initiated their research careers under his direction.
from 1878 to 1906. His interpretations of the luteo,
Jprgensen always preferred facts to bold hypotheses,
purpureo, roseo, praseo, violeo, croceo, flavo, and other and his controversy with Werner clearly reflects this
series of complex salts were made in the light of his
attitude. Niels Bjerrum (3) relates how Jprgensen
extensions and modifications of the famous chain reminded advanced students that although the atomic
theory (1, 2) proposed by the Swedish chemist, Chris- theory was a useful concept for correlating and ex-
tian Wilhelm Blomstrand (1826-1897).
plaining a large number of experimental facts, they
Jprgensen’s views remained essentially unchallenged ought not to think of atoms as actual objects.
until 1891 when the twenty-six-year-old Werner
Although not actually eloquent, Jprgensen could
published his “Beitrage zur Theorie der Affinitat und completely absorb his audience's attention when a
Valenz.” The subsequent controversy between the
subject caught his interest. For example, his lectures
two men forms an exciting chapter in the history of on Lavoisier’s life and work made a profound impres-
chemistry and still serves today as a fine example of an sion on his students. In his teaching, he consistently
ideal scientific discussion.
managed to convey to them not only a clear under-
Yet, despite the obvious importance of Jprgensen’s standing of chemistry, but also a love and respect for
work, no biographical data are available hi English the science.
with the exception of a short eulogy by one of his most
Through his textbooks, Jprgensen was able to extend
distinguished students, Niels Bjerrum (3). It is with his teaching influence far beyond the select circle of his
a view to filling this gap in the literature of the history
own students. These works reflect the same charac-
of chemistry that this paper is written. The biograph- teristic thoroughness that he expended in his laboratory
ical details are taken largely from three Danish articles
investigations. Probably his most famous text is
(4, 5, 6). “Kemiens Grundbegreben” (Fundamentals of Chem-
istry), published in 1902. In less than 200 pages,
Presented in part before the Division of the History of Chemistry Jprgensen gives not only a summary of the basic
of the American Chemical Society at the 133rd National Meeting, concepts of chemistry, but also a survey of its historical
San Francisco, California, April, 1958. development. This little classic has been translated
Volume 36, Number 10, October 1959 / 521
 Moissan, the Nobel prize laureate in chemistry for that
year, drafted a proposition to the Nobel committee
nominating J0rgensen for the next prize in chemistry.
Unfortunately, Moissan died later that year, and the
proposition was never submitted.

Nineteenth Century Chemical Confusion

In order to appreciate adequately the magnitude of
both Jprgensen’s and Werner’s achievements, we
must take into account the confused state of affairs in
which chemistry floundered during most of the nine-
teenth century. Various rival systems of chemistry
flourished. The dualistic theory of Berzelius, which
hitherto had been quite successful in the formulation
of inorganic compounds, was falling into disrepute as a
result of the inroads of the new organic chemistry.
No clear distinction was made between equivalent,
atomic, and molecular weights. It was only in 1858
that Cannizzaro's revival of Avogadro’s hypothesis
marked the beginnings of a consistent atomic weight
scale. When Cannizzaro spoke at Karlsruhe, Svante
Arrhenius had not yet been born. Indeed, years of
proselytizing by Arrhenius, van’t Hoff, and Ostwald
were to be necessary before the electrolytic dissociation
theory was finally accepted by the scientific world.
Sophus Mads Jorgensen (1837—1914), professor of chemistry in Copen- Thus, Werner’s view of the two types of linkage,
hagen (1871—1908). ("Proceedings of the Symposium on Co-ordination ionizable and non-ionizable, did much to clarify ideas
Chemistry, Copenhagen, Aug. 9—13, 1953/’ Danish Chemical Society, of chemical bonding a generation before the views of
Copenhagen, T954, p. 14.)
Kossel and Lewis (1916) led to our present concepts of
into several languages, among them German (1903), ionic and covalent bonding.
Italian (1904), Greek (1904), and English (1908). Today any chemist familiar with modern orbital
As a research worker, .Jorgensen was methodical, theory knows that nitrogen can form at most only four
deliberate, and careful. Although he could have dele- bonds. Armed with such knowledge, he might scoff
gated much routine work to assistants, he insisted on at the apparent naivete of Blomstrand and J0rgensen
personally performing all his analyses. In view of his whose structural formulas involved chains of ammonia
passion for perfection, his output was tremendous, and molecules containing quinquevalent nitrogen. Our
we are indebted to him for many of the basic experi- hindsight is always much better than our foresight.
mental facts of coordination chemistry. To mew the works of great men of the past in the light
In contrast, Werner was a rapid worker who preferred of modern knowledge is perhaps to belittle their
qualitative tests using porcelain plates and watch achievements. Thus, in evaluating the work of
glasses to more conventional quantitative methods. J0rgensen and Werner, we must preserve a sense of
Niels Bjerrum recalls the following incident typical of historical perspective.
Werner’s impulsive temperament. When Arthur Werner's coordination theory is familiar to most
Hantzsch, Werner’s professor, asked him, on short chemists and need not be elaborated here. However,
notice, for a paper describing the coordination theory, since j0rgensen’s interpretations were all based on the
Werner entered a room with a box full of cigars and now obsolete Blomstrand chain theory (1, 2), a few
did not Leave until the paper was written and the cigar remarks about this presently little known theory seem
box empty (3). in order.
Like many famous chemists, J0rgensen was not Odling (7) had proposed that the hydrogen atoms in
content merely to make original contributions in the ammonia could be replaced by metal atoms just as
laboratory, but was also keenly interested in the his- they were replaced by organic radicals in forming
torical development of chemistry, especially in Den- amines. As an extension of this idea, Blomstrand
mark. His studies in this field are characterized by suggested that these ammonia molecules could link
the same enthusiasm and thorough workmanship together as —Nil,— chains, analogous to —CH2—
shown in his laboratory investigations. Unfortunately, chains in hydrocarbons.
few of these studies have been published. The number of ammonia molecules associated with
Jorgensen’s strong sense of history caused him to the metal, i.e., the length of the chain, depended upon
view Werner's new theory as an unwarranted break in the metal and its valence. This point was later ac-
the development of the theories of chemical structure. counted for more adequately by Werner’s concept of
He regarded it as an ad hoc explanation insufficiently the coordination number. Blomstrand also made pro-
supported by experimental evidence. vision for different reactivities of various atoms and
Although unjustly neglected today, Jorgensen’s groups. Thus, halogen which could be precipitated
work aroused great interest among his contemporaries. by silver nitrate was called “farther,” while that which
In 1906 the French Academic des sciences presented could not was called “nearer,” a close approximation
him with its Lavoisier medal. Early in 1907 Ilenri of Werner’s later concept of outer and inner spheres.
522 / Journal of Chemical Education
Jorgensen’s Work Type MAf—Hexammines (Luteo Salts),
LI/(AT/jJfJ.Yo. During the first half of the nineteenth
Although Jprgensen created no new structural theory
of his own, he logically and consistently extended and century, measurement of vapor density was the only
method for determination of molecular weights. Until
modified Blomstrand’s chain theory to interpret the
the classical studies of Raoult and van’t Hoff about
many new series of complex compounds which he had 1882 on colligative properties of solutions, no reliable
succeeded in preparing for the first time. Just as
method existed for the determination of molecular
astronomers tried to force an explanation for the mo-
tion of the planets in terms of the Ptolemaic theory by weights of non-volatile compounds. Thus, cobalt(III)
chloride was thought to have the composition Co2CL
postulating more and more complicated epicycles, so
(by analogy with volatile Fe2Cl*), and hence cobalt
J0rgensen, in his attempts to account for his newly ammines were considered dimers. J0rgensen (8) in
prepared compounds from a unified theoretical point of 1890 and Petersen (9) in 1892 deduced evidence for
view, strained the theory of his mentor Blomstrand to
monomeric molecular weights by freezing point and
the breaking point. In 1891 the Copernican figure of
Alfred Werner appeared on the scene to challenge the conductivity measurements of such solutions, and
Blomstrand’s original formulas were halved. Thus,
old system with a radically new theory based, by
luteo cobaltic chloride, originally written C02CL 12NH»,
Werner’s own admission, upon the sturdy foundation of
was henceforth written Co CL 6NH3. The concept
J0rgensen’s painstaking experimental investigations. of octahedral configuration based on coordination
Indeed, J0rgensen’s work bore the seeds of the Blom- number six was a fundamental postulate of Werner’s
strand- J0rgensen theory’s destruction, for many of the
theory from its inception. It is possible that without
compounds first prepared by him later proved instru-
mental in demonstrating the validity of Werner’s J0rgensen’s halving of Blomstrand’s formulas, this
views. One is tempted to compare this situation with theory might never have been conceived.
Luteo cobaltic chloride was found to be a stable
Priestley’s discovery of oxygen, which led to Lavoisier’s
classic experiments on the nature of combustion and to yellow-orange compound (10). In solution, all the
chlorine is immediately precipitated by silver nitrate.
the subsequent collapse of the Phlogiston theory.
Although ammonia is a base, treatment of luteo cobaltic
However, unlike Priestley, who staunchly defended this chloride with hydrochloric acid at 100°C does not
theory until his death, J0rgensen finally became con-
vinced of the correctness of Werner’s theory and
remove any ammonia. Furthermore, treatment of
the solid with sulfuric acid does not remove any ammo-
graciously acknowledged its worth.
nia, but yields the compound Co2(S04)3112NH3, i.e.,
J0rgensen’s research can be divided into seven groups. the chlorine atoms are replaced by sulfate groups.
The first (1866-1878) includes a few isolated papers and
his work on alkaloid polyiodides, while the other six Clearly, some sort of very stable metal-ammonia, but
much less stable metal-chlorine bonding is indicated in
(1878-1906) constitute the work for which he was luteo cobaltic chloride. Blomstrand proposed the
famous—his investigations of metal-ammine complexes.
These studies, entitled “Beitrage zur Chemie der symmetrical formula
Kobaltammoniakverbindungen” (eight papers), “Bei- NH, Cl
trage zur Chemie der Chromammoniakverbindungen” NHj—NHj—Cl
NHj-NHs-Cl
(ten papers), “Beitrage zur Chemie der Rhodiumam- NH,—NH.,—Cl
moniakverbindungen” (nine papers), “tiber Metall- NHj—NHj—Cl
diaminverbindungen” (seven papers), “Zur Konstitu- NH,—NIL—Cl
INTI,
tion der Platinbasen” (four papers), and “Zur Konsti- On heating, however, one-sixth of the ammonia is
tution der Kobalt-, Chrom-, und Rhodiumbasen”
lost, and only two-thirds of the chlorine in the resulting
(eleven papers) appeared in various publications of the purpureo cobaltic chloride can now be precipitated by
Videnskabern.es Selskab, then in the Journal fiir prak- silver nitrate:
tische Chemie, and after 1S92 in the newly founded
Zeitschrift fiir anorganische Chemie. Indeed, the for- A
tunate subscriber to this new periodical had a ringside [Co(NH3)6]C13-- [Co(NH3)sC1]C12 + NHs
seat for the battle between J0rgensen and Werner. Removal of two ammonia molecules from Blomstrand’s
In the following comparison between J0rgensen’s formula for the luteo salt results in a structure which
work and that of Werner, we shall concern Lute on does not sufficiently account for the great difference
octahedral hexacovalent ammines of cobalt(III).1 between the two types of chlorine atoms in the purpureo
The survey is organized on the basis of compound type, salt. Therefore, J0rgensen proposed the following
rather than in strict chronological sequence. First to symmetrical formula for the luteo salt
be considered is type MAf in which the coordination
number of the central metal atom is satisfied by six NH,-Cl
NH3—NH3—Cl
ammonia molecules. We shall then proceed to replace NH3—NH3—NHa—Cl
Co2
the ammonia molecules one at a time with other groups, NHs—NHa—NH3—Cl
giving one example from each type.2 NHs—NHj—Cl
NH,—Cl

postulating that halogen atoms which are bound to the

1
Chapter 2 of J. C. Bailar’s “The Chemistry of the Coordina- metal atom through other groups such as ammonia can
tion Compounds,” Reinhold Publishing Corp., New York, 1956, be precipitated by silver nitrate, while those bound
has been a valuable source of information in the preparation of
this discussion. directly to the metal atom cannot (//). Since he
2
For a fuller discussion of Jprgensen’s life and work, see later regarded four as the maximum number of ammonia
Kauffman, G. B., Chymia, 6 (1960). molecules that could enter into a chain and since he

Volume 36, Number 10, October 1959 / 523

regarded such a chain as a particularly stable arrange- to the metal atom. The structures proposed by these
ment, Jdrgensen (12) subsequently modified this two investigators,
formula to
NHa—Cl Co—NH3—NH3—NH,—NHj—Cl
NHs—Cl
N Hj—N Ha—NHs—N H,—Cl NTT,—Cl
Co2
NH3—NHj—NHs—NHj—Cl Jdrgensen
NHS—Cl
NHS—Cl Cl H++
NH3 | NH3
Henceforth, all his structural formulas will show this
four-ammonia chain although his original proposals
were slightly different. Both J0rgensen’s3 and Wer- NHj I NHj
Cl
NHj
,NTTj Werner
Co—NHs—NHS—NHs—NHj—Cl
^NHs—Cl are both compatible with the experimental facts but
J0rgensen differ again in the mode of attachment of the “reactive”
NHs chlorine atoms. Jdrgensen regarded these atoms as
NHs | NH: linked to the metal atom through ammonia molecules,
while Werner considered them as not linked to any
particular atom, but attracted to the complex cation
NHs | NHj as a whole by electrostatic forces.
NHs Werner explained the formation of the purpureo salt
Werner
from the luteo salt by evolution of ammonia as a
ner's structures arc compatible with the experimental conversion of one of the three chlorine atoms from a
observations but differ in that Jdrgensen regarded the primary (ionic) to a secondary (non-ionic) valency.
chlorine atoms as attached to the metal atom through The entrance of the negative chlorine into the complex
ammonia molecules, while Werner regarded them as cation lowers the charge of the latter by one, and the
ionic—“at large,” so to speak—a concept considered charge of the resulting complex cation is now two,
quite revolutionary at that time. Werner also re- rather than three. Jdrgensen criticized this interpre-
garded the central metal atom and the ammonia mole- tation, arguing that if a given negative group is coor-
cules as comprising a discrete unit, a complex cation. dinated to the central metal atom, it cannot simul-
Such a structure should yield four ions in solution, taneously satisfy one of the primary valencies of the
and this was later confirmed by the conductivity metal (15), a point which Werner (16) later clarified.
studies of Werner and Miolati (IS). Werner’s structure requires that a solution of purpureo
Type MA;>B—Pentammines (Purpureo Salts), cobaltic chloride furnish three ions, a fact confirmed
[M(NH3)sX~d]Y3-u. The term purpureo (purple) is by the conductivity studies of Werner and Miolati (13).
derived from the color of purpureo cobaltic chloride, Type MAtBz—Tetrammines. These compounds may
be regarded as luteo salts in which one-third of the
[Co(NHs)sCl]Cl2, the substance with which Jdrgensen
began his research on complexes. This compound is ammonia has been replaced by other groups. It is
formed by heating luteo cobaltic chloride, among such compounds that we first encounter the
possibility of stereoisomerism.
A _
Cis- and trans- Dichlorobis(ethylenediamine) Salts
(Co(NHs)6]Ch-- [Co(NH3)6Cl]Cli + NHs (10)
>100°C (Violeo and Praseo Salts), [M{C2Hi(NH2)2}2Ch]X.
The best known example of cis-trans isomerism among
and thus purpureo salts were regarded by Jdrgensen as inorganic complexes was first observed by Jprgensen
luteo salts in which one-sixth of the ammonia had been not among simple tetrammines, but among salts in
replaced by halogen. The ammonia molecules are which the four ammonia molecules have been replaced
quite strongly bound to the cobalt atom in the purpureo by two molecules of the bidentate organic base, ethyl-
salt as shown by the fact that ammonia is not evolved enediamine (17). He evaporated an aqueous solution
even on heating to 100°C. Furthermore, Jdrgensen of the green compound, praseo cobaltic chloride
showed that cold concentrated sulfuric acid did not [Co{C2H4(XH2)2}2Cl2]Cl, and obtained an isomeric
react with the ammonia in the salt but yielded the com- violet compound which he called violeo cobaltic chlo-
pound [Co(NH8)5C1]S04, which, although it contained ride. Treatment of the violeo compound with hydro-
chlorine, gave no immediate precipitate with silver chloric acid regenerates the original praseo compound.
nitrate. He also found that only two-thirds of the Two-thirds of the chlorine in these compounds is
chlorine in the original salt could be immediately pre- “masked” but becomes ionic in solution as a result of
cipitated by silver nitrate, while the remaining third aquation (18).
was precipitated only on long boiling (1J). J0rgensen also prepared other members of the praseo
To account for this difference in reactivity, Jdrgen- (green) and violeo (violet) series as well as many
sen suggested, as did Werner after him, that the “unre- ethylenediamine derivatives of platinum. He re-
active” or “masked” chlorine was bound directly garded the difference in color as due to structural iso-
merism connected with the linking of the two ethylene-
3
For simplicity, monomeric formulas will be used for the re-
diamine molecules. Werner, on the other hand, be-
mainder of this discussion although they were not used by Jdr- lieved these compounds to be stereoisomers, i.e., com-
gensen until 1890. pounds with the same atoms and bonds but differing

524 / Journal of Chemical Education

only in the orientation of these atoms and bonds in So far we have seen how J0rgensen’s and Werner’s
space: formulations for metal-hexammines, pentammines, and
tetrammines, both systems reasonably compatible with
Cl c,h4 experimental facts, permitted two rival hypotheses to
/ / \ exist side by side for a limited time. However, the
Co—NH2—NHa—NHS—NHa—Cl scientific mind feels uneasy at accepting two alternative
\ \ /
Cl CaH4 explanations for a given group of phenomena, the coex-
Video istence of the wave and corpuscular theories of light
Cl C,H4 notwithstanding. As more experimental evidence ac-
Co—NH—NHj—NHS—NHi—Cl cumulated, the scales began to tip in favor of Werner’s
theory.
^Cl C,H,"'^ When successive ammonia molecules in a hexammine
Praseo are replaced by negative groups such as chlorine atoms,
Jorgensen these enter the coordination sphere and thus become
non-ionic or “masked.” With the replacement of the
Cl first two ammonia molecules, the ionic character of the
NH, Cl
compounds as predicted by the two theories is in com-
CUT,. Co plete agreement, but with that of the third ammonia
V
NH; 1 NH,
CT molecule, the ionic character of the resulting compounds
differs radically according to the two theories:
/C2H4
nh2 /NH,—Cl
Violeo (cis; 1, 2) Co N H, -N H3—N Hj—N H3—Cl
C1 "'N H3—Cl Four Ions [Co(NH3)6]CI3
NH, NH, 1—NH3
—NH,
C,H4 Co
/C!
.C,H4 CP Co—NHj—NH3—NHj—NH3—Cl
\L XNH3—Cl [Co(NH3)sC1]C12
NH,
k Cl
j. —NHj Three ions
—NH3
Praseo (trans; 1,6)
Co—Cl
Werner
nN H, NHa—N Ha—N Ha—Cl [Co(NHa)4Cl,]Cl
\ —NHa Two Ions
—NHa
According to Werner, this isomerism was merely a /C1
Co—N Ha—NHa—N Ha—Cl
geometric consequence of the octahedral structure and Non-
should be observed in compounds of type MA.iB2 ""'Cl Two Electrolyte[Co(NHa)3Cl3]0
Ions
which do not contain ethylenediamine. Thus, his J0rgensen Werner
theory would predict the existence of a series of violeo
(m-dichlorotetrammineeobalt(III)) salts, [Co(NH3)4- Jprgensen predicted that the chain of four ammonia
C12]C1, isomeric with the corresponding praseo (trans)
molecules would merely be shortened by one and the
compounds. However, replacement of both nitro
resulting compound would be similar to the preceding
groups in flavo (cfs-dini trotetramminecobalt (111 )) salts one in forming two ions in solution, one of the chlorine
with chlorine using dilute hydrochloric acid always
atoms still remaining ionic. On the other hand,
resulted in formation of the praseo (trans) compounds.
Werner (23) predicted an abrupt change in properties.
Naturally, J0rgensen, being a confirmed empiricist, The resulting compound should be a non-electrolyte
criticized Werner’s theory on the ground that it implied soluble in non-polar solvents, and such solutions should
the existence of such unknown series of compounds.
not conduct an electric current. Werner pointed out
The apparent non-existence of a violeo (cfs-dichlorotet-
that the properties of such compounds agreed with his
ramminecobalt(III)) series, however, represented only theoretical predictions. Jdrgensen (12) protested that
a temporary victory for Jprgensen since this series was
the very few triammine complexes of trivalent metals
finally discovered by Werner (19), who also subse- then known were too poorly characterized to allow any
quently explained the formation of trans compounds conclusions to be drawn.
from cis compounds by a theory of rearrangements (20).
The classical conductivity studies of Werner and
Werner further predicted that as a consequence of its Miolati (13) on a wide variety of metal-ammine com-
asymmetric octahedral structure, the violeo salt should
exist in enantiomorphic forms. Cfs-dichlorobis(ethyl- plexes agreed very well with Werner’s theory. The
conductivities of compounds such as [Co(NH3)3(N02)3]
enediamine)cobalt(III) chloride was finally resolved were found to be extremely low, an indication of non-
into its optical antipodes by Werner (21) in 1911 and
later by Bailar and Auten (22). electrolytic character. Petersen (24) verified Werner
and Miolati’s experiments but objected to their con-
Type M .4,/?,—Triammines, [M(Ar//3)3A3]°. These clusions in those cases where the conductivities corre-
compounds may be regarded as luteo salts in which
one-half of the ammonia has been replaced by other sponded to a greater number of ions than that, predicted
by the coordination theory. Werner explained these
groups. This type of compound played a most prom-
inent role in the supersession of the Blomstrand- apparent, discrepancies by aquation reactions such as
Jdrgensen chain theory by the Werner coordination [Co(NHs)j(NOj)5C1]
0
-I- H,0 —
+
theory. [Co(NH3)3(NO,),(H20)] + C1-.

Volume 36, Number 10, October 1959 / 525

However, measurements of compounds not containing by both. Although not all Jdrgensen’s criticisms
as ligands groups readily displaced by water agreed were valid, Werner, in many cases, was forced to
completely with the theory. Petersen also tried to modify various aspects of his theory. However, the
verify his conductivity measurements by cryoscopic basic postulates were verified in virtually every par-
studies, but lie encountered some discrepancies. Jdr- ticular.
gensen (IS) seized upon these in an attempt to discredit Although Werner’s ideas eventually triumphed,
the entire conductivity method and hence all of Werner Jdrgensen’s experimental observations are thereby
and Miolati’s results. Actually, Petersen’s results in no way invalidated. On the contrary, his experi-
did not support Jdrgensen's view any better than they ments, performed with extreme care, have proven com-
did Werner's theory. pletely reliable and form the foundation not only of the
Conclusion Blomstrand-Jdrgensen theory, but of Werner’s as well.
From the very beginning of the controversy, Werner
It was only natural that Werner’s views, marking a continually acknowledged his great debt to the older
sharp break in the classical theory of valency and man. For example, in 1913, on his return to Zurich
structure, should have seemed too radical to Jdrgensen. from Stockholm where he had received the Nobel prize,
When Werner first proposed his theory, the octahedral Werner addressed the Kemisk Forening in Copenhagen,
configuration for cobalt(III) was a mere guess without acknowledging the important role that Jdrgensen’s
adequate experimental verification. At this time, on experimental contributions had played in the develop-
the other hand, the older man had already devoted ment of the coordination theory. Unfortunately,
many years to thorough investigations of metal-ammine Jdrgensen’s grave and final illness prevented the meet-
complexes and had accounted for his findings by a ing of the two great adversaries.
consistent application of Blomstrand’s chain theory, Eduard Far ber, on the occasion of the hundredth
which he modified, but only when absolutely necessary. anniversary of Wilhelm Ostwald’s birth, discusses
However, when Werner (19) in 1907 finally succeeded Ostwald’s twofold division of scientific genius (80).
in preparing the missing violeo (cis) series of dichlorotet- This dichotomy seems particularly applicable to
ramminecobalt(III) salts whose existence was a
Jdrgensen and Werner. In Jdrgensen, the conserva-
necessary consequence of his theory, but not of Blom- tive, we have the classic type, the slow and deep-digging
strand’s, Jdrgensen promptly acknowledged the validity completer who produces with long deliberation and
of Werner’s views. slowly develops a traditional theory to new conse-
Another necessary consequence of the octahedral quences. In Werner, the liberal, we have the romantic
configuration was the fact that compounds of type type, the impulsive and brilliant initiator who pro-
M(AA)», i.e., compounds in which the coordination duces prolifically and easily at an early age. Each
number of the central metal ion is fulfilled by three needs the other. Science has need of both.
symmetrical chelate groups (which can only span cis
positions), should be optically active. When Werner
in 1912 succeeded in resolving into optical antipodes Acknowledgment
compounds of type [M{C2H4(NH2)2)a]Xn of cobalt(III) The author wishes to acknowledge the assistance of
(25), chromium(III) (26), and rhodium(III) (27), the Professor Niels Bjerrum of the Kgl. Veterinaer-og
correctness of Werner’s views became all the more
Landbohfyskoles Icemiske Laboratorium, Kdbenhavn, in
apparent to Jdrgensen. Yet because of the prevalent locating the Danish biographical articles. He is also
view that optical activity was connected with carbon indebted to Finn Inge Gr0nberg of Fresno State Col-
atoms, a number of Werner’s contemporaries objected lege for help in translating these.
that the optical activity was due to the ethylenedi-
amine molecules, even though these are optically inac-
tive. Finally, in 1914, when Werner (28) succeeded in Literature Cited
resolving the completely inorganic compound dodecam- (1) Blomstrand, C. W., “Die Clsemie dev Jetztzeit von Stand-
mine-fi-hexol-tetracobalt(III) bromide punkte der elektrochemischen Auffassung aus Berzelius
Lehre entwickelt,” Heidelberg, 1869.
OH
(2) Blomstrand, C. W., Ber., 4, 40 (1871).
[Co{<^Co(NH3),)3]Br6, (3) Bjerrum, N., “Proceedings of the Symposium on Co-
OH ordination Chemistry, Copenhagen, August 9-13, 1953,”
Danish Chemical Society, Copenhagen, 1954, p. 12.
using silver dextro-a-bromocamphor-7r-sulfonate, even (4) Veibel, S., in “Dansk Biografisk Leksikon,” Vol. 12,
his most sceptical opponents were silenced, and the Schultz Forlag, Copenhagen, 1937, p. 251.
octahedral configuration of cobalt(III) was unequivo- (5) S0rensen, S. P. L., Fysisk Tids., 12, 217 (1913-14).
(6) S0RENSEN, S. P. L., Oversigt over Videnskabemes Selskabs
cally established. Ironically, this compound, which Forhandlinger, 46 (1914).
forged a crucial link in the proof of Werner’s coordination (7) Odling, W., Chem. News, 21,289 (1870).
theory, was first prepared by Jdrgensen (£0), the fore- (8) J0RGENSEN, S. M., J. prakt. Chem., [2] 41,429 (1890).
most exponent of the rival Blomstrand chain theory. (9) Petersen, E., Z. physik. Chem., 10, 580 (1892).
The conti oversy between Jdrgensen and Werner (10) J0rgensen, S. M., Z. anorg. Chem.., 19, 78 (1899).
(11) J0ruensen, S. M., J. prakt. Chem., [2] 35, 417 (1887).
over the constitution of metal-ammine complexes pro-
(12) J0RGENSEN, S. M., 7.. anorg. Chem., 5, 147 (1894).
vides us with an excellent illustration of the synergism (13) Werner, A. and Miolati, A., Z. physik. Chem., 12, 35
so often encountered in the history of science. During (1893); 14,506(1894); 21,225(1896).
the course of this competition, conducted without any (14) J0rgensen, S. M., J. prakt. Chem., [2] 18, 209 (1878).
trace of jealousy or rancor, each chemist did his ut- (15) J0rgensen, S. M., Z. anorg. Chem., 19, 109 (1899).
(16) Werner, A., Ber., 46, 3674 (1913); 47, 1964, 1978 (1914).
most to prove his views, and in the process a tremen- (17) J0rgensen, S. M., J. prakt. Chem., [2] 39, 1 (1889); [2J
dous amount of fine experimental work was performed 41,440(1890).
526 / Journal of Chemical Education
(18) J0rgensen, S. M., ibid., [2] 27, 433 (1883). (24) Petersen, E., Z. physik. Chem., 22, 410 (1897).
(19) Werner, A., Ber., 40, 4817 (1907). (25) Werner, A., Ber., 45, 121 (1912).
(20) Werner, A., Ann., 386, 1 (1912). (26) Ibid., p. 865.
(21) Werner, A., Ber., 44, 3279 (191!). (27) Ibid., p. 1228.
(22) Bailar, J. C-, and Atjten, R. W., ./. Am. Chem. Soc., 56, (28) Werner, A., Ber., 47, 3087 (1914).
774 {1934); Bailar, J. C., Inorg. Syntheses, 2, 222 (1946). (29) J0rgensen, S.M., Z. anorg. Chem., 16, 184 (1898).
(23) Werner, A., Z. anorg. Chem., 3, 267 (1893). (30) Farber, E., J. Chem. Educ., 30, 600 (1953).

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