Preparation of Nickel Carbonyl

Preparation of Nickel Carbonyl. Perform the experiment in the presence of your instructor Work in a fume cupboard Nickel carbonyl is extremely poisonous ) 

Assemble an apparatus as showm in Fig. 137. Fill the gas meter with pure carbon monoxide and charge a Kipp gas generator for 

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Fig. 14.15. Preparation of nickel carbonyl at different temperatures and milling conditions according to Heinicke et al. [10],...

II. Preparation of Ammonium Hexafluocobaltate(II) (248). 12. Preparation of Hexaaminenickel(II) Chloride (248). 13. Preparation of Nickel Carbonyl (249). 

Fig. 345. Apparatus for the preparation of nickel carbonyl, carbonyl hydrides, and nitroyl carbonyls, b shaking vessel from Fig. 344 k condensing traps...

Ma.nufa.cture. Nickel carbonyl can be prepared by the direct combination of carbon monoxide and metallic nickel (77). The presence of sulfur, the surface area, and the surface activity of the nickel affect the formation of nickel carbonyl (78). The thermodynamics of formation and reaction are documented (79). Two commercial processes are used for large-scale production (80). An atmospheric method, whereby carbon monoxide is passed over nickel sulfide and freshly reduced nickel metal, is used in the United Kingdom to produce pure nickel carbonyl (81). The second method, used in Canada, involves high pressure CO in the formation of iron and nickel carbonyls the two are separated by distillation (81). Very high pressure CO is required for the formation of cobalt carbonyl and a method has been described where the mixed carbonyls are scmbbed with ammonia or an amine and the cobalt is extracted as the ammine carbonyl (82). A discontinued commercial process in the United States involved the reaction of carbon monoxide with nickel sulfate solution. 

Tetramethylcyclobutadiene dichloride [76404-16-5] can be prepared by reaction of nickel carbonyl and 3,4-dichlorotetramethylcyclobutene (CBD) in polar solvents (103). The complex is black-violet, mp 185°C (dec). 

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. 

Reaction of l,3-bis(phenylmethyl)imidazol-2-ylidene with nickel tetra carbonyl gives [(t (C)-1,3-bis(phenylmethyl)imidazol-2-ylidene)Ni(CO)3] (970M2472). Complexes of composition [Ni(CO)2L2] with imidazol-2-ylidenes are also known (93JOM(459)177). Another species to be mentioned in this respect is bis(l,3-dimesitylimidazol-2-ylidene)nickel(0) (94JA4391). 1,3-Dicyclohexylimidazol-2-yUdene substitutes triphenylphosphine or THF from [NiX LJ (X = Cl, Br L PPhj, THF) to yield the stable nickel(II) complexes 69 (X = C1, Br R = Cy) (97OM2209). Another preparation of nickel(II) derivatives is the interaction of... 

As, for the most part, the corresponding ester derivatives are a more important synthetic target, recent literature has demonstrated methods to prepare the esters directly. Examples include the use of nickel carbonyl in a methanol/dimethylformamide solvent system(37) the direct conversion of benzyl alcohol to methylphenyl-acetate using cobalt carbonyl(38) and a reaction system which utilizes an ammonium salt bound to an organic polymer(39). 

Tetrakis[phosphorus(III) chloride] nickel has been prepared by the reaction of nickel carbonyl with phosphorus-(III) chloride at room temperature.1 The synthesis of this compound as described below is based on this method. 

Polymerization was carried out in benzene in the presence of bis-(7r-allylnickel halides). The latter were prepared from nickel carbonyl and allyl halide (allyl bromide, crotyl chloride, bromide, or iodide etc.). The results of the polymerization runs are reported in Table I. The data indicate that all of the bis(7r-allylnickel halides) initiate by themselves the stereospecific butadiene polymerization yielding a polymer with 97-98% 1,4-units. The cis-l,4/trans-l,4 ratio depends on the halide in the dimeric r-allylnickel halide but not on the nature of allylic ligand. The case of bis(7r-crotylnickel halides) shows the effect of halide on microstructure, for whereas (C4H7NiCl)2 initiates cis- 1,4-polybutadiene formation, trans-1,4 polymers are produced by (C4H7NiI)2. The reactivity increase in the series Cl < Br < I. 

Recently, a nickel zeolite hydrogenation catalyst has been prepared by a novel route (94) involving the adsorption and decomposition of nickel carbonyl onto NaX, which would not be expected to result in the formation of acid sites. In general, the platinum metal-containing zeolites are more active than those containing other transition metals. For example, in zeolite Y the following activity series has been found,... 

The reagent is prepared by the reaction of dimelhylamine with n-butyllithium in n-hexane at 0°. An ethereal solution of nickel carbonyl is added to an ethereal suspension of lithium dimethvlamide below 10° and the mixture is stirred for I hr. 

The carboxylic acids 432 were prepared from the bromopyrido[2,l-i>]-quinazolinones 431 by the modified Cassar method, with carbon monoxide in 5% aqueous dimethylformamide under 40 psi pressure, or by the use of an equimolar amount of nickel carbonyl in the presence of calcium hydrox-... 

Preparation. The complex is prepared by the reaction of nickel carbonyl with acrylonitrile.1... 

Ever since Parkyns (60) prepared nickel particles on oxide (A1203, Si02) surfaces by decomposition of nickel carbonyl, metal cluster compounds (alkoxides, carbonyls, organometallics, etc.) have been used increasingly for the production of laboratory metal catalysts (Table I), and several reviews have appeared on this subject (6l-65a,b). 

Nickel, cobalt, and iron catalysts are cmnmonly used for the Fischer-Tropsch s thesis. Nickel catalysts have been prepared by precipitation from a nitrate solution with potassium carbonate in the presence of thoria and kieselguhr in the proportions lOONiilSThOzilOO kieselguhr. It is not desirable to employ nickel catalysts at low temperatures and elevated pressures because the formation of nickel carbonyl is excessive. In the temperature range of 170-220°C at. low pressures, both liquid and gaseous products are obtained. As the temperature is increased to 300-350°C and the pressure increased to 300-400 psi, nickel catalysts produce only methane. Thus, these catal nsts can be used for making a gas from coal comparable in heating value to natural gas. 

There are three industrially important methods by which monomeric esters of acrylic acid, CHj=CH—COOR, can be prepared, altiiough many other processes have been suggested. The first one, which is described here, is based on the Ileppe reaction of acetylene, carbon monoxide, and an alcohol in the presence of nickel carbonyl and an acid such as hydrochloric acid (Fig. 15-38) ... 

The heterocyclic biphosphine (CF3 P-CF2)2 (for preparation see p. 250) displaces 2 moles of carbon monoxide from an excess of nickel carbonyl to give an unstable product thought to be (CF3-P-CF2)a Ni(CO)3 2. ... 

The substitution of CO in metal carbonyls by olefinic and acetylenic compounds is one of the chief methods for preparing tt complexes of transition metals. Unfortunately this procedure fails almost completely when applied to nickel carbonyl, and this may be one of the reasons why until recently no tt complexes of nickel with olefinic or acetylenic ligands were known. The reasons for this behavior of nickel carbonyl will become clearer, if both its electronic structure and the mechanism of the ligand exchange reactions are considered. 

The substitution of the carbonyl groups of Ni(CO)4 by other two-electron ligands remains the principal method of preparation of nickel complexes with carbonyl ligands. The 15-crown-5 ether-triarylphosphine hybrid ligands, 1 and 2, have been used to prepare the corresponding Ni(GO)3L complexes." ... 

AH the common monobasic (107) and dibasic esters (108) of tetrahydrofurfuryl alcohol have been prepared by conventional techniques the dibasic esters and some of the mono esters are effective as primary or secondary plasticizers for vinyl polymers. Tetrahydrofurfuryl acrylate [2399-48-6] and methacrjiate [2455-24-5] specialty monomers, have been produced by carbonylation (nickel carbonyl and acetylene) of the alcohol (109) as weU as by direct esterification (110—112) and ester interchange (111). 

The preparation of 7,7-d2-cholesterol in 1950 was the first example of deuterium incorporation into steroids via desulfurization of mercaptals with deuterated Raney nickel. A substantially modified version of this reaction subsequently became the first widely used method for site-specific insertion of two deuteriums in place of a carbonyl oxygen. This conversion consists of the preparation of a mercapto derivative (84 85), which usually... 

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