Nickel tetracarbonyl preparation

The phase-transfer catalysed reaction of nickel tetracarbonyl with sodium hydroxide under carbon monoxide produces the nickel carbonyl dianions, Ni,(CO) 2- and Ni6(CO)162, which convert allyl chloride into a mixture of but-3-enoic and but-2-enoic acids [18]. However, in view of the high toxicity of the volatile nickel tetracarbonyl, the use of the nickel cyanide as a precursor for the carbonyl complexes is preferred. Pretreatment of the cyanide with carbon monoxide under basic conditions is thought to produce the tricarbonylnickel cyanide anion [19], as the active metal catalyst. Reaction with allyl halides, in a manner analogous to that outlined for the preparation of the arylacetic acids, produces the butenoic acids (Table 8.7). 

Ni(CO)4 is the sole binary carbonyl complex of the elements of group 10 that is stable (Table 8.1). However, very few studies in which Ni(CO)4 is used in the preparation of catalysts have been reported [43]. This is probably due to the difficulty of manipulation of Ni(CO)4 and its very high toxicity. However, surface Ni(CO)4 species have been identified after the interaction of CO with highly dispersed supported nickel catalysts prepared by other routes [44]. Recent interest in the use of Ni(CO)4 has focused on the controlled production of nickel nanoparticles for specific purposes, such as in automotive converters [45]. The use of nickel tetracarbonyl as an agent for the nucleation process in the growth of single-wall carbon nanotubes has also been reported [46]. 

Nickel tetracarbonyl was prepared first in 1888 by Mond and Langer by passing carbon monoxide over finely divided nickel. It is the most important zero valent compound of nickel and is used industrially to make high-purity nickel powder and pellets and to produce nickel coatings on steel. 

Nickel tetracarbonyl may be prepared in the laboratory by the Hieber process, a disproportion reaction of several nickel compounds of organic thio acids, such as nickel(II) phenyldithiocarbamate, (CeHs— NH—C(=S)—S)2Ni, with carbon monoxide under controlled conditions. In such disproportionation reactions, the divalent nickel ion converts to a tetravalent nickel complex (Hieber. H. 1952. Z.anorg.Chem., 269, pp. 28). The overall reaction is ... 

Nickel tetracarbonyl is a highly toxic volatile colorless liquid that is shipped in cylinders pressurized with carbon monoxide.8 Its vapor is about six times as dense as air. Purification of nickel by the Mond process is based on the decomposition of Ni(CO)4, the reverse of Eq. 15.3. The yellow-red iron pentacarbonyl slowly decomposes in air and is sensitive to light and heal. In feet. Fe-jfCOJy, an orange solid, is prepared by photolysis of Fe(CO). ... 

Nickel(IV) sodium paraperiodate 1-hydrate (amt.) analysis of, 6 203 Nickel tetracarbonyl, 2 234 Niobium(V) fluoride, 3 179 Nitramide, 1 68, 72 Nitrates, preparation of anhydrous, 5 38... 

Scheme 1.2 Preparation of ( y5-cyclopentadienyl)(jy3-cyclopentenyl)nickel(II) from nickel tetracarbonyl via the nickel(0) complex Ni(C5H6)2 as the supposed intermediate...

Although nickel tetracarbonyl, iron pentacarbonyl, and diiron enneacarbonyl were already prepared in the 1890s, more than three decades passed before the chemistry of transition metal carbonyls took off. Undoubtedly, some parts of the chemical community had recognized that compounds such as Ni(CO)4 and Fe(CO)5 deserved special attention, in particular due to the use of Ni(CO)4 for the production of pure metallic nickel. However, since the structure of those compounds was unknown, transition metal carbonyls remained, more or less, a curiosity. 

Many derivatives of nickelocene can be prepared. A particularly useful reaction is that between nickelocene and nickel tetracarbonyl, leading to [C6H5NiCO]2 and (C6H5)3Ni3(CO)2. ... 

Halogen bridged, dimeric 7r-allynickel halides. III, were first described by Fischer and Burger, who prepared them in low yields by the reaction of nickel tetracarbonyl with allylic halides (9, 10),... 

Nickel tetracarbonyl undergoes a rapid oxidative addition of the Si-Si bond of 1, highly strained fluorinated disilane, at room temperature to give ffve-membered cyclic bis(organosilyl)nickel(II) complex 2, which then reacts with terf-buty-lacetylene to give six-membered disilacyclohexadiene derivatives 3 as a mixture of the regioisomers (Eq. 1) [10]. A similar bis-silylation reaction of alkynes with bis(organosilyl)nickel(II) complex has been reported in the reaction of bis(trichlorosilyl)(bipy)nickel(II) (bipy 2,2 -bipyridyl), which is prepared by dialkyl(bipy)nickel(II) with trichlorosilane [11]. 

The compound [Ni(TTN)]a can be prepared by reacting TTN with excess nickel tetracarbonyl in benzene (Equation 5). The dark brown-red amorphous material, insoluble in common organic solvents, exhibits no carbonyl stretching frequencies but four strong TTN bands at 1528(s), 1338(s), (1320(sh)), 1185(m), and 800(m) cm in the IR spectrum. A new band also is observed at 965 cm which can be attributed to C S bonds. The polymeric chain-like structure 3 was proposed for [Ni(TTN)],. 

The method of transferring to ampoules may be made much simpler if complete freedom from suspended oxidation product is not required. A series of ampoules may be prepared, each filled with dry carbon dioxide, and the liquid nickel tetracarbonyl simply poured into them (hood with good draft). Then the nickel tetracarbonyl is frozen, and the ampoules are sealed. 

Such aspects of metal carbonyl structure may be explained by consideration of the coordination number of the central metal atom as an important factor in determining the stability of metal carbonyls. As is the case with other transition metal derivatives such as the ammines, octahedral hexa-coordinate metal carbonyl derivatives seem to be especially favored. Thus, hexacoordinate chromium hexacarbonyl is obviously more stable and less reactive than pentacoordinate iron pentacarbonyl or tetracoordinate nickel tetracarbonyl. Moreover, hexacoordinate methylmanganese pentacarbonyl is indefinitely stable at room temperature (93) whereas pentacoordinate methylcobalt tetracarbonyl (55) rapidly decomposes at room temperature and heptacoordinate methylvanadium hexacarbonyl has never been reported, despite the availability of obvious starting materials for its preparation. 

In a recent note, brick-red crystals prepared from triphenylpropenyl halides and nickel tetracarbonyl are tentatively suggested to be /x-halogeno-bis-TT-triphenylpropenyldinickel dicarbonyl 42a). 

A bis-Wittig reaction was used to prepare the polycyclic system (202). Cyclo-octatetraene (203) was obtained by dimerization of an o-bis(l-oxo-2-butynyl)arene in the presence of nickel tetracarbonyl (8... 

Quinone complexes may be prepared either from acetylenes or from the quinone itself (see Figure 74). With nickel tetracarbonyl, most quinones react forming salt-like complexes which are best formulated as the oxidation products Ni2+ (quinone)2 [43,44]. These complexes are paramagnetic, insoluble and hydroscopic and do not behave like those others where the quinone is ni-bonded to the nickel. Tetramethylquinone (duro-quinone), which is a less oxidizing quinone, reacts readily with nickel tetracarbonyl forming the diamagnetic, red bis-duroquinone nickel, 8.12, m.p. 205° [48]. 

Preparation. High purity nickel can be produced through electrolytic process or by the carbonyl process. In the latter case carbon monoxide reacts at 50°C with impure Ni (or nickel-copper matte) to give the volatile tetracarbonyl from which the metal (99.9-99.99% purity) is obtained by decomposition at 200-230°C through the reaction ... 

Salts of the dianion [Ni6(CO)12]2- have been prepared by reduction of tetracarbonyl nickel under a variety of experimental conditions with yields seldom exceeding 40 to 50%.1,2... 

Several compounds of iron and carbon monoxide are known. Mond and Quincke6 were the first to obtain experimental evidence of the existence of volatile iron carbonyls they succeeded in volatilising reduced iron in a current of carbon monoxide to a very slight extent, and concluded that a tetracarbonyl, Fe(CO)4, had been produced corresponding to the nickel analogue, Ni(CO)4, which had been prepared the previous year.7 A few months later Mond and Danger 8 succeeded m isolating the iron carbonyl, and found it to be not the tetra but the penta derivative. 

The lack of any knowledge on the structure and bonds of these compounds was responsible for the poor results. In fact, when tetracarbonyl-nickel was first prepared, Werner s theory had not as yet been postulated, and even later the theory was not extended to the carbonyls because they were considered anomalous compounds, owing to their chemical and physical properties. 

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