The Discovery of Nickel

He made another observation with the new mineral. After weathering, green spots had been formed on the mineral surface. He scraped the green stuff off and roasted it to oxide at red heat. This he mixed with charcoal and heated in a crucible to a high temperature. A metal with no resemblance to copper was formed. The metal was white and had slight magnetic properties. 

In the same year, 1751, Cronstedt also investigated Kupfemkkd from Freiberg in Germany, isolated a metal from it and found exactly the same properties as in the metal from Loos. After further studies of the physical, chemical and magnetic properties of his new metal he published the discovery in the Transactions of The Royal Swedish Academy of Sciences in 1751 and 1754 and he proposed the name nidcel for the new element. 

It is interesting to notice that two Swedes, Brandt and Cronstedt, who each discovered a new element and chose their names, did not hesitate to select the negatively loaded names cobalt and nickel. In our modern technological society the names of these metals have clearly positive connotations because of their functions in important alloys. 

Opinions differ about which mineral in Loos Cronstedt used for his nickel discovery. Was it 

Cronstedt himself describes the mineral as Niccolum ferro el cobalto arsenicatis el sul-phuratis. This may indicate that it was gersdorffite that Cronstedt had found on his visit to Loos in 1751. Erland Grip [31.1] says that ...in gersdorffite from Loos in 1751 the Swedish chemist A. F. Cronstedt discovered the element nickel . 

---

Since the discovery of nickel carbonyl in 1890 (15), carbonyls of many other metals have been prepared. Nickel and iron are the only metals that combine direcdy with CO to produce carbonyls in reasonable yields. At least one carbonyl derivative is known for every t5 -block metal. A number of the neutral complexes that have been reported ate Hsted in Table 4. 

In the years since the discovery of nickel and iron in the catalytic centres, numerous different descriptions of the catalytic cycle of hydrogenase have been proposed. These were based on different oxidation states of the metal centres, and different sequences of transfer of electrons and hydrous. Although the reaction cycle has not been definitively resolved, the spectroscopic evidence places constraints on possible models that should be considered. 

Nickel in Meteorites. Centuries before the discovery of nickel, primitive peoples shaped meteoric iron into implements and swords and appreciated the superiority of this Heaven-sent metal (125). In 1777 J. K. F. Meyer of Stettin noticed that when he added sulfuric acid to some native iron which P. S. Pallas had found in Siberia, he obtained a green solution which became blue when it was treated with ammonium hydroxide. In 1799 Joseph-Louis Proust detected nickel in meteoric iron from Peru (126). This grayish white native iron had been observed by Rubin de Celis. Since it did not rust, it was sometimes mistaken for native silver. 

In 1890, Ludwig Mond, Carl Langer, and Friedrich Quincke (24) announced the discovery of nickel carbonyl, Ni(CO)4. The unusual properties of this carbonyl stimulated a great deal of interest and investigation into other carbonyls and in 1908, Mond, Hirtz, and Cowap (25) described cobalt carbonyl. They found (26) by cryoscopic measure-... 

The subsequent story of manganese is associated with T. Bergman who by that time had already confirmed the discovery of nickel. He characterized pyrolusite in the following way the mineral called black magnesium is a new earth it should not be confused either with roasted lime or with magnesium alba (i.e. magnesium oxide). However, T. Bergman failed to separate the metal from pyrolusite, in contrast to I. Kaim. 

As the reverse reaction proceeds when nickel carbonyl is heated at a temperature of 150°C or more, the formation and decomposition reactions of nickel carbonyl began to be utilized in the manufacture of highly pure nickel [79a]. Following the discovery of nickel carbonyl, iron carbonyl (Fe(CO)5) [84] was found in 1891, and various other kinds of metal carbonyls have now been found [80a]. 

Nickel(II) dithiocarbamate complexes have been known for nearly a century, while since the late 1960s, nickel(TV) complexes have been prepared. These were soon followed by the discovery of nickel(III) complexes, the first crystal-lographically characterized example coming only in 1990 (1465). Most recent work has served to expand these areas, while electrochemical generation of unstable nickel(I) species has also been documented (1466) and the synthesis of a nickel(I) nitrosyl complex has been claimed (379). 

Acetylene-Based Routes. Walter Reppe, the father of modem acetylene chemistry, discovered the reaction of nickel carbonyl with acetylene and water or alcohols to give acryUc acid or esters (75,76). This discovery led to several processes which have been in commercial use. The original Reppe reaction requires a stoichiometric ratio of nickel carbonyl to acetylene. The Rohm and Haas modified or semicatalytic process provides 60—80% of the carbon monoxide from a separate carbon monoxide feed and the remainder from nickel carbonyl (77—78). The reactions for the synthesis of ethyl acrylate are... 

Fischer-Tropsch Synthesis The best-known technology for producing hydrocarbons from synthesis gas is the Fischer-Tropsch synthesis. This technology was first demonstrated in Germany in 1902 by Sabatier and Senderens when they hydrogenated carbon monoxide (CO) to methane, using a nickel catalyst. In 1926 Fischer and Tropsch were awarded a patent for the discovery of a catalytic technique to convert synthesis gas to liquid hydrocarbons similar to petroleum. 

Beranger, G., Duffaut, F., Morlet, J. and Tiers, J.F. (1996) A Hundred Years after the Discovery of Invar ... the Iron-Nickel Alloys (Lavoisier Publishing, Paris). 

The discovery of a new heterodinuclear active site in [NiFe] hydro-genases opens the way for the proposal of catalytic cycles based on the available spectroscopic data on the different active site redox states, namely EXAFS studies that reveal that the Ni-edge energy upon reduction of the enzyme supports an increase in the charge density of the nickel (191). 

Recent discoveries have expanded the utility of nickel-catalyzed coupling reactions. Inclusion of butadiene greatly improves the efficiency of the reactions.268... 

Several combinatorial approaches to the discovery of transition metal based catalysts for olefin polymerization have been described. In one study Brookhart-type polymer-bound Ni- and Pd-(l,2-diimine) complexes were prepared and used in ethylene polymerization (Scheme 3).60,61 A resin-bound diketone was condensed with 48 commercially available aminoarenes having different steric properties. The library was then split into 48 nickel and 48 palladium complexes by reaction with [NiBr2(dme)] and [PdClMe(COD)], respectively, all 96 pre-catalysts being spatially addressable. 

Just a few years after the discovery of the deposition and electroactivity of Prussian blue, other metal hexacyanoferrates were deposited on various electrode surfaces. However, except for ruthenium and osmium, the electroplating of the metal or its anodizing was required for the deposition of nickel [14], copper [15,16], and silver [9] hexacyanoferrates. Later studies have shown the possibilities of the synthesis of nickel, cobalt, indium hexacyanoferrates similar to the deposition of Prussian blue [17-19], as well as palladium [20-22], zinc [23, 24], lanthanum [25-27], vanadium [28], silver [29], and thallium [30] hexacyanoferrates. 

CRG [Catalytic Rich Gas] A process for making town gas and rich gas from light petroleum distillate (naphtha). The naphtha is reacted with steam over a nickel-alumina catalyst yielding a gas mixture rich in methane. Developed by British Gas and used in the United Kingdom in the 1960s, but abandoned there after the discovery of North Sea gas. In 1977,13 plants were operating in the United States. 

Mercury and nickel salts form many stable complexes with biologically important molecules such as those containing sulphydryl groups Chapter 5 stresses the importance and the dangers of these being formed in the skin from topical contact. The last 10 years have been a highly fertile and productive period in the discovery of antibacterial quinolones (reviewed in Chapter 6) which inhibit target enzymes at the molecular level. 

---