Celebrating Todd Marder: 65th Birthday and His Contributions to Inorganic Chemistry.

Professor Todd B [...].

Chemical Research and Instruction in Zürich, 1833-1872.

The development of universities and technical schools in nineteenth century Switzerland is commonly assumed to be similar to the development of comparable schools in Germany. To a large extent this is correct, but there are subtle differences in the founding and organization of Swiss institutions that are reflective of the Swiss national and local cantonal contexts. In the case of Zürich, the specific local political and financial conditions underlying the formation of the University of Zürich, the Zürich Cantonal School and the Swiss Federal Polytechnic resulted in a complex set of dual appointments and shared facilities that were absent at comparable chemical laboratories at German universities. This essay outlines the origins of these complex relationships under Carl Löwig (1833-1853) and Georg Städeler (1853-1870) and follows in more detail the complex career path of Johannes Wislicenus in Zürich from his appointment as Privatdozent in 1860 to his appointment as Director of the Polytechnic in 1871. Wislicenus' career path illustrates the institutional context of chemistry in Zürich and shows how this context, including the roles of cantonal and federal support, and the physical constraints created by shared laboratory facilities, shaped chemical research and instruction in Zürich.

Alfred Werner's role in the mid-20th century flourishing of American inorganic chemistry.

The development of organic and physical chemistry as specialist fields, during the middle and end of the 19th century respectively, left inorganic behind as a decidedly less highly regarded subfield of chemistry. Despite Alfred Werner's groundbreaking studies of coordination chemistry in the early 20th century, that inferior status remained in place - particularly in the US - until the 1950s, when the beginnings of a resurgence that eventually restored its parity with the other subfields can be clearly observed. This paper explores the extent to which Werner's heritage - both direct, in the form of academic descendants, and indirect - contributed to those advances.

Stereochemistry of coordination compounds. From alfred werner to the 21st century.

As a contribution to the scientific symposium, November 22nd, 2013, commemorating the Nobel Prize awarded to Alfred Werner in 1913, a presentation of the development of stereochemistry of coordination compounds during the past 120 years was given. Stereochemistry was fundamental to Werner's theory of coordination compounds. After Werner's death in 1919, stereochemistry in this field did not progress much further for almost 20 years, but then developed continuously. It was realized that stereochemical features of elements showing coordination numbers larger than four are responsible for an almost unlimited number of stereochemical possibilities, thus opening a molecular world of new structures. In the beginning of the 21st century, interest in the field rose again considerably, mainly due to the potential of stereoselective catalysis, and the self-assembly of supramolecular structures. An end of these developments is not in sight. Here an abbreviated version of the lecture is given. A PowerPoint(®) file, or a video of the presentation, can be downloaded.

Alfred Werner's chemistry of dinuclear complexes--a test case of Werner's intuition.

The re-investigation of four original tris-bridged dinuclear dicobalt complexes from the Werner collection of the University of Zurich by X-ray diffraction studies is described. The complex [Co2(NH3)6(µ-NH2) (µ-OH)(µ-O2)](NO3)3 was studied recently. As the most interesting feature it was found to contain a µ-superoxo bridge, recognized by Alfred Werner and his coworker as an asymmetric peroxo bridge. The newly established µ-mono- and diacetato structures from crystals of the Werner collection, [Co2(NH3)6(µ-OH)2(µ-O2CMe)](NO3)3·H2O and [Co2(NH3)6(µ-OH)(µ-O2CMe)2](NO3)3·H2O, were assigned by Alfred Werner and his co-workers as mono- or di-bridged systems with the water functioning as η(1)-aqua ligands and not, as revealed by the X-ray diffraction studies, as solvate molecules. Similarly the exact nature of the µ(N, O) nitrito bridge in the structure of the [Co2(NH3)6(µ-OH)2(µ-O2N)](NO3)3·H2O complex from the Werner collection was left open in Werner's and his coworker's description. Only the accuracy of the X-ray diffraction study could ascertain any earlier 'good guess'. The assignment of the bridges of bridged dinuclear structures at Werner's time are well conceived considering the lack of appropriate analytical tools. The structural assignments of Alfred Werner for the discussed dinuclear complexes are therefore considered to deviate only marginally from the real structures. They are testimonies of Alfred Werner's predictive abilities in coordination chemistry supported by his prepared mind, his great abilities of intuition and conceptual thinking.

The color of complexes and UV-vis spectroscopy as an analytical tool of Alfred Werner's group at the University of Zurich.

Two PhD theses (Alexander Gordienko, 1912; Johannes Angerstein, 1914) and a dissertation in partial fulfillment of a PhD thesis (H. S. French, Zurich, 1914) are reviewed that deal with hitherto unpublished UV-vis spectroscopy work of coordination compounds in the group of Alfred Werner. The method of measurement of UV-vis spectra at Alfred Werner's time is described in detail. Examples of spectra of complexes are given, which were partly interpreted in terms of structure (cis ↔ trans configuration, counting number of bands for structural relationships, and shift of general spectral features by consecutive replacement of ligands). A more complete interpretation of spectra was hampered at Alfred Werner's time by the lack of a light absorption theory and a correct theory of electron excitation, and the lack of a ligand field theory for coordination compounds. The experimentally difficult data acquisitions and the difficult spectral interpretations might have been reasons why this method did not experience a breakthrough in Alfred Werner's group to play a more prominent role as an important analytical method. Nevertheless the application of UV-vis spectroscopy on coordination compounds was unique and novel, and witnesses Alfred Werner's great aptitude and keenness to always try and go beyond conventional practice.

A refuge for inorganic chemistry: Bunsen's Heidelberg laboratory.

Immediately after its opening in 1855, Bunsen's Heidelberg laboratory became iconic as the most modern and best equipped laboratory in Europe. Although comparatively modest in size, the laboratory's progressive equipment made it a role model for new construction projects in Germany and beyond. In retrospect, it represents an intermediate stage of development between early teaching facilities, such as Liebig's laboratory in Giessen, and the new 'chemistry palaces' that came into existence with Wöhler's Göttingen laboratory of 1860. As a 'transition laboratory,' Bunsen's Heidelberg edifice is of particular historical interest. This paper explores the allocation of spaces to specific procedures and audiences within the laboratory, and the hierarchies and professional rites of passage embedded within it. On this basis, it argues that the laboratory in Heidelberg was tailored to Bunsen's needs in inorganic and physical chemistry and never aimed at a broad-scale representation of chemistry as a whole. On the contrary, it is an example of early specialisation within a chemical laboratory preceding the process of differentiation into chemical sub-disciplines. Finally, it is shown that the relatively small size of this laboratory, and the fact that after ca. 1860 no significant changes were made within the building, are inseparably connected to Bunsen's views on chemistry teaching.

[The scientific career of Scheele cannot be reduced to chlorine discovery]. / La découverte du chlore ne saurait résumer l'oeuvre de Scheele.

The life of this poor pharmacist and very efficient man of science was made of many encounters: meeting with pharmacy, meeting with chemistry, meeting with prestigious scientists, meeting with chlorine, meeting with oxygen, meeting with organic chemistry, etc. This chemist devoid of money, working with rudimental apparatus did discover chlorine but he also discovered oxygen before Priestley, unfortunately he did not publish his results in time. He isolated also many organic acids and even glycerol, before the rising of organic chemistry.

Ferrocentric memories of Edward I. Stiefel.

A brief memorial, from the ferrocentric view of science, about E.I. Stiefel's discovery of heme, maxi-ferritins in bacteria, recognition of the relationship to animal maxi-ferritins, and other reminiscences of ferritin defined as a storage battery.

[Regarding respiration and the so-called "animal heat." An historical sketch]. / En torno a la respiración y al llamado calor animal. Bosquejo histórico.

According to Aristotle and Galen, the essential function of the respiration phenomenon was to cool the blood. Towards the middle of the XVI Century, Miguel Servet suggested, in his treatise Christianismi restitutio..., that the inspired air could have other functions besides cooling the blood. Later, Joseph Black thought that respiration was a combustion. In the light of the advances in chemistry achieved in the XVII Century, the English scientist Adair Crawford and the French chemist Antoine-Laurent Lavoisier conceived, in the second half of that century, the first general and quantitative theories on the origin of animal heat. Both these authors had the conviction that the "inflammable element", which will be called oxygen, was not formed in the pulmonary territory, but could be absorbed by the blood. Oxygen, foreseen by Mayow at the end of XVII Century, was discovered by Joseph Priestley in 1774. Lavoisier gave the name of oxygen to this gas and firmly established that the respiration phenomenon consists essentially in a process of combustion. The mathematician Joseph-Louis Lagrange, native of Turin, suggested that animal heat originates in all breathing tissues. This phenomenon was verified and described in detail by the biologist Lazzaro Spallanzani, professor at the University of Pavia. Dissemination, in the scientific world, of the new chemical nomenclature and of the respiratory theory, closely related to it, was based fundamentally on the works "Méthode de nomenclature chimique..." (1787) and "Traité élémentaire de chimie..." (1789). During the XIX Century, studies on the phenomenon of animal respiration continued and fundamental discoveries in this subject were attained, such as conversion of hemoglobin to oxyhemoglobin once oxygen had been fixed. Now it is possible to study the regulating mechanisms of the energetic metabolism of the myocardium in vivo, which allows decisive interventions in certain cardiopathies, such as in acute ischemic cardiopathy.