Essay
Alfred Werner: A Forerunner to Modern Inorganic Chemistry
Prof. em. Dr. Helmut Werner,
Corresponding Author
Prof. em. Dr. Helmut Werner
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)Search for more papers by this authorProf. em. Dr. Helmut Werner,
Corresponding Author
Prof. em. Dr. Helmut Werner
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)
Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg (Germany)Search for more papers by this authorGraphical Abstract
Numerous honors were bestowed on Alfred Werner, who in 1913 was the first Swiss scientist to be awarded the Nobel Prize in Chemistry. This Essay gives an overview of Werner′s scientific work and its significance beyond coordination chemistry. Picture: gray Co, red O, blue N, yellow H.
References
- 1L. Horner, Helv. Chim. Acta 1967, 50, Supplement 1, 93–116.
- 2Evidence for this was the decision to do his PhD research under the supervision of Arthur Hantzsch and the titles of his first publications as well:
- 2a“Über die räumliche Anordnung der Atome in stickstoffhaltigen Molekülen” (On the Spatial Orientation of Atoms in Nitrogen-Containing Molecules): A. Hantzsch, A. Werner, Ber. Dtsch. Chem. Ges. 1890, 23, 11–30;
10.1002/cber.18900230104 Google Scholar
- 2b“Bemerkungen über stereochemisch isomere Stickstoffverbindungen” (Comments on Stereochemically Isomeric Nitrogen Compounds): A. Hantzsch, A. Werner, Ber. Dtsch. Chem. Ges. 1890, 23, 1243–1253;
10.1002/cber.189002301201 Google Scholar
- 2c“Über ein zweites Benzoinoxim”(On a Second Benzoin Oxime): A. Werner, Ber. Dtsch. Chem. Ges. 1890, 23, 2333–2236;
10.1002/cber.18900230299 Google Scholar
- 2d“Über zwei stereochemisch isomere Derivate des Furfuraldoxims” (On Two Stereochemically Isomeric Derivatives of Furfural Oxime): A. Werner, Ber. Dtsch. Chem. Ges. 1890, 23, 2336–2339.
10.1002/cber.189002302100 Google Scholar
- 3
- 3aG. B. Kauffman indicated that 45 of Werner's 173 publications focused on topics in organic chemistry.[4] Even five decades after they had been published, his papers on the mechanism of the Walden inversion[3b,c] are still state of the art.
- 3bA. Werner, Ber. Dtsch. Chem. Ges. 1911, 44, 873–882;
- 3cpages 68–72 in A. Werner, Justus Liebigs Ann. Chem. 1912, 386, 1–272.
- 4G. B. Kauffman, J. Chem. Educ. 1966, 43, 155–156.
- 5Over the years, I have been asked several times, particularly by non-German speeking colleagues, whether I am a relative of Alfred Werner, which I had to deny. Sometimes the reason for the assumption was the similarity of the names of our birth places, whereby it was not noticed that I was born in Mühlhausen but Alfred Werner in Mulhouse (German name from 1871 to 1918: Mülhausen). Franz Hein, my first mentor, encouraged me already in the late 1950s to make enquiries regarding a relationship which, however, remained unsuccessful.
- 6
- 6aP. Karrer, Helv. Chim. Acta 1920, 3, 196–224;
- 6bFacsimilae: P. Karrer, Helv. Chim. Acta 1967, 50, Supplement 1, 7–23.
- 7 Albert Einstein chose to study at the Eidgenössische Polytechnikum for the same reason.[26
- 8G. B. Kauffman, Alfred Werner—Founder of Coordination Chemistry, Springer, Berlin, 1966.
10.1007/978-3-662-11104-8 Google Scholar
- 9Arthur Hantzsch (1857–1935) and Alfred Werner were good friends. The friendship also remained firm after Hantzsch (Professor at the Polytechnikum in Zürich since 1885) accepted the call to the University of Würzburg to succeed Emil Fischer (1852–1919) in 1893, and after he moved 10 years later to the University of Leipzig to succeed Johannes Wislicenus (1835–1902). Hantzsch and Werner corresponded regularly and, when possible, met several times each year. G. B. Kauffman, who had the chance to read letters sent from Hantzsch to Werner,[8] concluded that “despite Hantzsch’s more than five hundred publications, his greatest discovery was probably Alfred Werner”.
- 10Hantzsch’s esteem for Werner since the beginning of their collaboration is, for example, well manifested by Hantzsch’s decision to add to their first joint paper[2a] the postscript: “The undersigned only fulfills his obligation to fairness by declaring that, in the case that the results described above have important consequences of some kind, the theoretical framework published by himself and Mr. A. Werner is in all its decisive parts the intellectual property of Mr. Werner. He alone formulated the fundamental ideas with its important conclusions already at a time, when it was mentioned in vague comments from others, that nitrogen possibly could give geometrical isomers similarly to carbon.”
- 11“150 Jahre Chemie an der Universität Zürich”: C. H. Eugster, Chimia 1983, 37, 194–237.
- 12K.-H. Ernst, F. R. W. P. Wild, O. Bracque, H. Berke, Angew. Chem. 2011, 123, 10970–10977; Angew. Chem. Int. Ed. 2011, 50, 10780–10787.
- 13
- 13aG. B. Kauffman described Hantzsch as “slender, reserved, abstemius and controlled”, whereas Werner “inclined toward corpulence, was hearty and robustly humorous in company, well-known for his enjoyment of alcohol and tobacco, and at times impulsive”;
- 13bRef. [8], p. 16.
- 14E. Berl, J. Chem. Educ. 1942, 19, 153–154.
- 15The Schweizerische Schulrat was paramount to the rector’s office of the Eidgenössische Polytechnikum; and was in charge approving credits, confirming appointments, and awarding teaching qualifications. After the founding of the École Polytechnique Fédérale de Lausanne the Schweizerische Schulrat became in charge of both Federal Technical Universities.
- 16Ref. [8], p. 21.
- 17
- 17aIn German: “Die Affinität ist eine, vom Centrum des Atoms gleichmässig nach allen Teilen seiner Kugeloberfläche wirkende anziehende Kraft. Aus dieser Auffassung der Affinität folgt nothwendig, dass gesonderte Valenzeinheiten nicht bestehen. Die Valenz bedeutet eine von Valenzeinheiten unabhängiges, empirisch gefundenes Zahlenverhältniss, in welchem die Atome sich miteinander verbinden”. And as subscript: “Dem Einwurf, dass durch die Annahme von Valenzeinheiten die Zahlenverhältnisse, in welchem die Atome sich miteinander verbinden erklärt werden, muss entgegengehalten werden, dass eine derartige Vorstellung keine Erklärung sondern nur eine Umschreibung dieser Erscheinung bedeutet.
- 17bWerner's Habilitationsschrift is written in German Kurrentschrift and page 9 of it is reproduced in Kauffman’s monograph (Ref. [8], p. 22).
- 18
- 18aA. Werner, Ber. Dtsch. Chem. Ges. 1892, 25, 27–48;
10.1002/cber.18920250105 Google Scholar
- 18bA. Werner, Ber. Dtsch. Chem. Ges. 1893, 26, 1561–1567.
10.1002/cber.18930260273 Google Scholar
- 19Ref. [8], p. 23.
- 20The Polytechnikum as well as later the ETH was organized not in faculties but in divisions. The Laboratorium für Anorganische Chemie, of which the most prominent chairman was Gerold Schwarzenbach (1904–1978) in the second half of the 20th century, today belongs to the Department of Chemistry and Applied Biosciences.
- 21Starting in 1902, after the faculty had intervened and the cantonal administration had issued a decree, the main inorganic lecture was given by Werner and not by Abeljanz.[11]
- 22Ref. [8], pp. 77–80.
- 23This happened quite soon thereafter: In 1895 Hans von Pechmann received the call to the chair of chemistry at the University of Tübingen.
- 24
- 24aIn German: “.. äusserst primitiv und unzugänglich, …︁ die Doktoranden waren auf roh ausgebaute ehemalige Keller und Holzbehälter verwiesen, in denen auch um die Mittagsstunde künstliche Beleuchtung notwendig war …︁ Der kalte, zementierte Kellerboden, die schlechte Heizung und die Unmöglichkeit einer richtigen Ventilation machten diese Räume in hohem Grade ungesund. Sie verdienten den Namen Katakomben, den die Studierenden ihnen beigelegt hatten, mit vollem Recht”;
- 24bRef. [6], pp. 10–11.
- 25A. Werner, Z. anorg. Chem. 1893, 3, 267–330.
- 26G. Schwarzenbach, Helv. Chim. Acta 1967, 50, Supplement 1, 38–63.
- 27L. H. Gade, Chem. Unserer Zeit 2002, 36, 168–175.
- 28Paul Pfeiffer (1875–1951) did earned his PhD under the supervision of Alfred Werner in 1898. After he finished his dissertation entitled “Molekülverbindungen der Halogenide des 4-wertigen Zinns und der Zinnalkyle” (Molecular Compounds of the Halides of Tin(IV) and of Tin Alkyls), he worked for one semester with Wilhelm Ostwald at Leipzig and then with Arthur Hantzsch at Würzburg and returned to the University of Zurich for the Winter semester 1900/01. After he finished his Habilitation at Zurich one year later, he became Lecturer and was promoted to Associate Professor in Theoretical Chemistry in 1908. In rapid order, he became the Director of the Chemical Institutes at Rostock in 1916, at Karlsruhe in 1919, and at Bonn in 1922, where he stayed until his retirement in 1947.
- 29P. Pfeiffer, J. Chem. Educ. 1928, 5, 1090–1098.
- 30Paul Karrer mentioned that the unusually high number of female doctoral students and PhD chemists at that time was due to the fact that since the winter semester 1868/69 female students could immatriculate at the University of Zurich.[6]
- 31G. B. Kauffman, J. Chem. Educ. 1959, 36, 521–527.
- 32
- 32aIn German: “daß geistreiche Spekulationen nicht genügen, eine Theorie der Metallammoniaksalze a priori zu konstruieren. Erst ’dem unerbittlichen Versuche‘ wird es allmählich gelingen, über die verwickelten Verhältnisse dieser ausgedehnten Gruppe von Verbindungen Klarheit zu verbreiten”;[32b]
- 32bS. M. Jörgensen, Z. Anorg. Allg. Chem. 1894, 5, 147–196.
10.1002/zaac.18940050119 Google Scholar
- 33
- 33aOne of Werner’s “northern colleagues” once told him that it is not so wrong to describe his intuitively formulated ideas as an “ingenious impudence”;
- 33bRef. [8], p. 30.
- 34Nobel Lecture held December 11, 1913 in Stockholm; see: A. Werner, Helv. Chim. Acta 1967, 50, Supplement 1, 24–35.
- 35
- 35aThe French chemist E. Fremy, who studied extensively the chemistry of ammine metal complexes some decades prior to Jørgensen, characterized those ionic complexes according to their color as praseo, luteo, roseo, purpureo, violeo, and xantho salts; see:
- 35bE. Fremy, Ann. Chim. Phys. 1852, 35, 257–311;
E. Fremy, J. Prakt. Chem. 1852, 57, 81–106.
10.1002/prac.18520570113 Google Scholar
- 36L. H. Gade, Z. Anorg. Allg. Chem. 2012, 638, 247–248.
- 37P. Pfeiffer, Angew. Chem. 1920, 33, 37–39. This aspect was extensively discussed also by L. H. Gade.[27] The structure of the octahedral complexes drawn by Werner follow the ideas of van’t Hoff and Le Bel about the stereochemistry of the tetracoordinated carbon atom.
- 38S. M. Jörgensen, Z. Anorg. Allg. Chem. 1894, 7, 289–330.
- 39
- 39aA. Werner, A. Miolati, Z. Phys. Chem. 1893, 12, 35–55;
10.1515/zpch-1893-0103 Google Scholar
- 39bA. Werner, A. Miolati, Z. Phys. Chem. 1894, 14, 506–521.
- 40A. Werner, Z. Anorg. Allg. Chem. 1895, 8, 153–188.
- 41A. Werner, Ber. Dtsch. Chem. Ges. 1907, 40, 4817–4825.
- 42In a later publication (S. M. Jörgensen, Z. Anorg. Allg. Chem. 1899, 19, 109–157), Jørgensen denied any insulting intention of his statement.
- 43Werner was always careful to make sure that the objective differences with Jørgensen would not lead to personal disputes. Thus after receiving the Nobel Prize he attempted to visit Jørgensen in Copenhagen on his return from Stockholm to Zurich; however, this was not possible because Jørgensen was very ill.[6]
- 44
- 44aF. A. Cotton, J. Chem. Soc. Dalton Trans. 2000, 1961–1968;
- 44bB. Spingler, M. Scavany-Grigorieff, A. Werner, H. Berke, S. J. Lippard, Inorg. Chem. 2001, 40, 1065–1066;
- 44cE. Meggers, Eur. J. Inorg. Chem. 2011, 2911–2926.
- 45Ref. [12], p. 10972.
- 46A. Werner, A. Vilmos, Z. Anorg. Allg. Chem. 1899, 21, 145–158.
- 47King separated the enantiomers of [Co(en)2(NH3)Cl]2+ via the diastereomeric (+)-bromocamphersulfonates. The separation was achieved without problems and the racemization, which Werner initially was afraid of, did not occur: A. Werner, V. L. King, Ber. Dtsch. Chem. Ges. 1911, 44, 1887–1898.
- 48A. Werner, Ber. Dtsch. Chem. Ges. 1914, 47, 3087–3094.
- 49The special irony of this result is that the racemate of the tetranuclear complex was first prepared by Jørgensen: S. M. Jørgensen, Z. Anorg. Allg. Chem. 1898, 16, 184–197.
- 50See: http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1913/.
- 51Werner wrote in German: “…︁ gelangen wir zu einer neuen Definition für die Basen, dahingehend, dass die Basen Verbindungen sind, welche die Fähigkeit besitzen, die Wasserstoffionen des Wassers zu ketten und dadurch das Gleichgewicht zwischen dem Wasser und seinen Ionen durch Aufnahme von Wasserstoffionen zu stören, was eine Vergrösserung der Hydroxylionenkonzentration zur Folge hat.” See Ref. [34], p. 29.
- 52
- 52aA. Werner, Ber. Dtsch. Chem. Ges. 1905, 38, 914–921;
- 52bA. Werner, Ber. Dtsch. Chem. Ges. 1905, 38, 2022–2027.
- 53See also: G. B. Kauffman, Bull. Hist. Chem. 1997, 20, 50.
- 54U. Wannagat, Chem. Unserer Zeit 1967, 1, 24–27.
- 55G. N. Lewis, Valence and the Structure of Atoms and Molecules, The Chemical Catalog Company, New York, 1923.
- 56J. C. Bailar, Helv. Chim. Acta 1967, 50, Supplement 1, 82–92.
- 57In German: “..that Wernersche Ideen noch auf lange Zeit hinaus einen starken Einfluß auf die Entwicklung unserer Wissenschaft ausüben und diese mächtig fördern werden.”[37a]
