Werner, Alfred

▪ Swiss chemist

Introduction

born Dec. 12, 1866, Mulhouse, France

died Nov. 15, 1919, Zürich, Switz.

 Swiss chemist and winner of the Nobel Prize for Chemistry in 1913 for his research into the structure of coordination compounds (coordination compound).

Education

      Werner was the fourth and last child of Jean-Adam Werner, a foundry worker and former locksmith, and his second wife, Salomé Jeanette Werner, who was a member of a wealthy family. Alsace had become part of the second German Empire in 1871, but French continued to be spoken by the family. Although most of Werner's articles were published in German in German journals, his cultural and political sympathies remained with France.

      Although Werner's later interest in religion was minimal, his family was Roman Catholic, and he attended the École Libre des Frères (1872–78), followed by the École Professionelle, a technical school where he studied chemistry (1878–85). He spent one year (1885–86) of compulsory military service in the German army at Karlsruhe, where he audited chemistry lectures at the Technische Hochschule. In 1886 he enrolled in the Eidgenössisches Polytechnikum (now the Eidgenössische Technische Hochschule [ETH], or Swiss Federal Institute of Technology) in Zürich, from which he received a technical chemical degree (1889). Because the Polytechnikum was not empowered to grant the doctorate until 1909, Werner received a doctorate formally from the University of Zürich in 1890.

Early research

      Werner's first publication, a cornerstone of stereochemistry, based on his doctoral dissertation and written with his research supervisor, Arthur Hantzsch (Hantzsch, Arthur Rudolf), applied Joseph-Achille Le Bel (Le Bel, Joseph-Achille) and Jacobus Henricus van 't Hoff (Hoff, Jacobus Henricus van 't)'s concept of the tetrahedral carbon atom (1874) to the nitrogen atom. It explained numerous cases of cis-trans isomerism among trivalent nitrogen compounds such as the oximes, led to the discovery of new isomers, and placed the stereochemistry of nitrogen on a consistent theoretical foundation. During the winter semester of 1891–92, Werner worked on thermochemical studies at the Collège de France in Paris with Marcellin Berthelot (Berthelot, Pierre-Eugène-Marcellin).

      In 1892 Werner became a Privatdozent (unsalaried lecturer) at the Polytechnikum upon acceptance of his Habilitationsschrift (an original research paper required in order to teach at a university). In this work, which elicited little notice because it was published (1891) in an obscure local journal, he proposed replacing August Kekule (Kekule von Stradonitz, August)'s rigidly directed valence bonds in organic compounds with a more flexible approach of viewing affinity as a variously divisible force acting equally in all directions from the atom's centre.

Major theoretical work

      In 1893 Werner published his third major article on stereochemistry, setting forth his controversial theory of coordination compounds (coordination compound), which had occurred to him in a dream. Although his knowledge of inorganic chemistry was extremely limited, he awoke one night in 1892 at 2:00 AM with the solution to the puzzle of what were then called “molecular compounds.” He wrote his most important theoretical paper by 5:00 PM. It brought him almost instant fame and an appointment as extraordinarius (associate) professor at the University of Zürich, where he spent the rest of his career. In 1894 he became a Swiss citizen and married Emma Wilhelmina Giesker, with whom he had two children, Alfred and Charlotte. An enthralling lecturer and prolific researcher, he was promoted to full professor in 1895.

      At the time of its inception, Werner's theory was largely without experimental verification. He had done no work in the field, and the data that he cited in support of his ideas had been obtained by others, especially by his primary scientific adversary, the Danish chemist Sophus Mads Jørgensen. Jørgensen adhered to the rival Blomstrand-Jørgensen “chain theory,” which was eventually superseded by Werner's theory, the basis for modern coordination chemistry.

      Werner discarded Kekule's artificial distinction between “valence compounds,” amenable to classical valence theory, and “molecular compounds,” those not explainable by this theory. Among the latter were the metal-ammines, which contain a metal salt as well as ammonia (a neutral molecule), both of which were capable of independent existence. The basic property of the ammonia was “masked” in that it did not react with acids. Also, the nature of the strong bond between the metal salt and the ammonia was unexplained.

      Werner proposed a revolutionary approach in which the constitution and configuration of metal-ammines (now colloquially called “Werner complexes”), double salts, and metal salt hydrates were logical consequences of a new concept, the coordination number. He divided metal-ammines into two classes—those with coordination number six, for which he postulated an octahedral configuration, and those with coordination number four, for which he proposed a square planar or tetrahedral configuration. He also postulated two types of valence—primary valence, which bonded the anion to the metal atom, and secondary valence, which bonded the ammonia to the metal atom.

      Werner demonstrated the validity of his views by citing numerous reactions, transformations, and cases of isomerism. He showed that loss of ammonia from metal-ammines was not a simple loss but a substitution in which a change in function of the anions occurred simultaneously, resulting in a complete transition from cationic compounds through nonelectrolytes to anionic compounds. He also showed how ammonia could be replaced by water or other groups, and he demonstrated the existence of transition series between ammines, double salts, and metal hydrates. In addition, he speculated on other subjects such as the state of salts in solution and the polarization effects involved in chemical bonding.

Assessment

      Werner not only explained known coordination compounds but also predicted the existence of numerous series of unknown compounds, which were discovered by him and his students during a quarter-century tour de force of synthetic activity that confirmed his theory in almost every particular. His concepts of ionogenic and nonionogenic bonding adumbrated the current distinction between electrostatic and covalent bonding (covalent bond) by a full generation. His ideas soon encompassed almost the entire field of inorganic chemistry and even found application in organic, analytical, and physical chemistry, as well as biochemistry, geochemistry, and mineralogy. He was one of the first to show that stereochemistry is not limited to organic chemistry but is a general phenomenon. His coordination theory has had an effect on inorganic chemistry comparable to that exerted on organic chemistry by the ideas of Kekule, Archibald Scott Couper (Couper, Archibald Scott), Le Bel, and van 't Hoff. Consequently, he is sometimes called “the inorganic Kekule.”

      Following his resolution of series after series of coordination compounds beginning in 1911, Werner became the first Swiss chemist to win the Nobel Prize for Chemistry, “in recognition of his work on the linkage of atoms in molecules, by which he has thrown fresh light on old problems and opened new fields of research, particularly in inorganic chemistry.” Shortly thereafter he began to suffer from a general, progressive, degenerative arteriosclerosis, especially of the brain, aggravated by years of excessive drinking and overwork. He died in Burghölzli, a psychiatric hospital. He was not only the founder of modern inorganic stereochemistry but also one of the major chemists of all time.

George B. Kauffman

Additional Reading

George B. Kauffman, Alfred Werner: Founder of Coordination Chemistry (1966), is the only book-length biography. George B. Kauffman, “Foundation of Nitrogen Stereochemistry,” Journal of Chemical Education, 43(3):155–165 (March 1966), is an annotated English translation of Werner's doctoral dissertation with detailed discussion. George B. Kauffman, Classics in Coordination Chemistry, Part 1: The Selected Papers of Alfred Werner (1968), contains edited and annotated English translations with commentary of six of Werner's most important theoretical and experimental papers, including his coordination theory; it also includes a brief biography.George B. Kauffman

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