Rhenium, discovery

Element No 43 they named masurium after the region of Masuria in the German province of Eastern Prussia (now Mazury in Poland), from where Walter Noddack originated. Rhenium they named after the river Rhine and the home region of Ida Tacke. The rhenium discovery could be verified, but not the masurium discovery. No evidence of masurium was given besides the three X-ray lines in Table 28.2. Was masurium the final erroneous conclusion in the dramatic story of the discovery of eka-manganese, element 43 ... 

L. Rhenus, Rhine) Discovery of rhenium is generally attributed to Noddack, Tacke, and Berg, who announced in 1925 they had detected the element in platinum ore and columbite. They also found the element in gadolinite and molybdenite. By working up 660 kg of molybdenite in 1928 they were able to extract 1 g of rhenium. 

Ethylene oxide (qv) was once produced by the chlorohydrin process, but this process was slowly abandoned starting in 1937 when Union Carbide Corp. developed and commercialized the silver-catalyzed air oxidation of ethylene process patented in 1931 (67). Union Carbide Corp. is stiU. the world s largest ethylene oxide producer, but most other manufacturers Hcense either the Shell or Scientific Design process. Shell has the dominant patent position in ethylene oxide catalysts, which is the result of the development of highly effective methods of silver deposition on alumina (29), and the discovery of the importance of estabUshing precise parts per million levels of the higher alkaU metal elements on the catalyst surface (68). The most recent patents describe the addition of trace amounts of rhenium and various Group (VI) elements (69). 

The isolation and identification of 4 radioactive elements in minute amounts took place at the turn of the century, and in each case the insight provided by the periodic classification into the predicted chemical properties of these elements proved invaluable. Marie Curie identified polonium in 1898 and, later in the same year working with Pierre Curie, isolated radium. Actinium followed in 1899 (A. Debierne) and the heaviest noble gas, radon, in 1900 (F. E. Dorn). Details will be found in later chapters which also recount the discoveries made in the present century of protactinium (O. Hahn and Lise Meitner, 1917), hafnium (D. Coster and G. von Hevesey, 1923), rhenium (W. Noddack, Ida Tacke and O. Berg, 1925), technetium (C. Perrier and E. Segre, 1937), francium (Marguerite Percy, 1939) and promethium (J. A. Marinsky, L. E. Glendenin and C. D. Coryell, 1945). 

The discovery of the elements 43 and 75 was reported by Noddack et al. in 1925, just seventy years ago. Although the presence of the element 75, rhenium, was confirmed later, the element 43, masurium, as they named it, could not be extracted from naturally occurring minerals. However, in the cyclotron-irradiated molybdenum deflector, Perrier and Segre found radioactivity ascribed to the element 43. This discovery in 1937 was established firmly on the basis of its chemical properties which were expected from the position between manganese and rhenium in the periodic table. However, ten years later in 1937, the new element was named technetium as the first artificially made element. 

The development of chemistry itself has progressed significantly by analytical findings over several centuries. Fundamental knowledge of general chemistry is based on analytical studies, the laws of simple and multiple proportions as well as the law of mass action. Most of the chemical elements have been discovered by the application of analytical chemistry, at first by means of chemical methods, but in the last 150 years mainly by physical methods. Especially spectacular were the spectroscopic discoveries of rubidium and caesium by Bunsen and Kirchhoff, indium by Reich and Richter, helium by Janssen, Lockyer, and Frankland, and rhenium by Noddack and Tacke. Also, nuclear fission became evident as Hahn and Strassmann carefully analyzed the products of neutron-bombarded uranium. 

Recently, researchers have built on the discovery of a class of novel 188Re cyclized peptides that exhibit high melanoma tumor uptake and good pharmacokinetics by designing analogs containing non-radioactive rhenium and an appended DOTA BFCA to act as a carrier for radiolanthanides.18... 

Existence of technetium was predicted from the vacant position in the Periodic Table between manganese and rhenium. Noddack, Tacke, and Berg reported its discovery in 1925 and named it masurium. The metal actually was never isolated from any source by these workers. Its existence, therefore, could not be confirmed. Perrier and Segre in 1937 produced this element by bombarding molybdenum metal with deuterons in a cyclotron. They named the element technetium derived from the Greek word technetos, meaning artificial. 

Rhenium is a rare element, having eluded discovery until 1925. Its chemistry [1, 2] and electrochemistry [3, 4] have been reviewed on previous occasions. The properties of Re compounds closely parallel those of Tc, and, although many comparative studies have been conducted on the two elements, the rhenium literature is the more extensive. The properties of both elements are quite distinct from those of manganese. 

Rapid development of this area followed the discovery of routes to these complexes, either by ready conversion of terminal alkynes to vinylidene complexes in reactions with manganese, rhenium, and the iron-group metal complexes (11-14) or by protonation or alkylation of some metal Recent work has demonstrated the importance of vinylidene complexes in the metabolism of some chlorinated hydrocarbons (DDT) using iron porphyrin-based enzymes (15). Interconversions of alkyne and vinylidene ligands occur readily on multimetal centers. Several reactions involving organometallic reagents may proceed via intermediate vinylidene complexes. 

The photochemistry of rhenium complexes occupies a prominent position in the photochemistry of transition metal complexes. Along with early preparative studies on photosubstitution of carbonyl species like Re(CO)sX, the preparation of the remarkably stable yellow complex /ac-Re(CO)3(phen)Cl foreshadowed the discovery of the a large class of related luminescent materials by Wrighton and co-workers in the 1970s [ 1 ]. As pointed out by Vogler and Kunkley, the current photochemistry of rhenium complexes is rich, spanning eight oxidation states from formal Re(0) (for example, Re2(CO)io) to formal Re(VII) (for example MeReOs) [2],... 

There are many similarities to the case of Marie and Pierre Curie, and their experience with the manufacturing of radium, to draw from the successful discovery of rhenium the emphasis on the analytical enrichment procedure, the determination to produce weighable samples, the art of taking patents and mastering the production of the new element and, last but not least, the writing of a monograph on... 

On several occasions, letters were sent to the couple asking whether the discovery had received confirmation or not. [51] Walter Noddack just kept silent, and even more and more silent as the years went by. The Noddacks felt they were unable to provide any kind of proof. Not only were they unable to show a sample of masurium which would have, as had been the case for rhenium, closed the controversy on the existence of the element, but even the original photographic plate of typical spectral lines was never shown as a piece of evidence. [52]... 

J.G.F. Druce, Rhenium. Dvi-Manganese, the Element of Atomic Number 75 (Cambridge Cambridge University Press, 1948), on 1-4, lists several alleged discoveries Davyum, ilmenium, lucium, nipponium for element... 

This collaboration was actually established by an industrial research contract, signed on 18 June 1925, K. U. Leuven Archives, Noddack-Tacke Papers, 107. The opportunity to patent their discovery had not escaped the team since they wrote patents on their own. See the list of thermocouple patents, ca. 1923, K. U. Leuven Archives, Noddack-Tacke Papers, 108. As a consequence of their contract, the rights of the Nod-dacks patent for the extraction of rhenium from manganese ores is held by Siemens und Halske. See J.F.G. Druce, Rhenium,... 

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