Nickel carbonyl preparation

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). 

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. 

Ni(CO)4 is a most important nickel carbonyl compound and can even be prepared directly from its constituents yet the corresponding palladium... 

Symmetrical ketones can be prepared in good yields by the reaction of organo-mercuric halides with dicobalt octacarbonyl in THF, or with nickel carbonyl in DMF or certain other solvents. The R group may be aryl or alkyl. However, when R is alkyl, rearrangements may intervene in the C02(CO)g reaction, though the Ni(CO)4 reaction seems to be free from such rearrangements. Divinylic ketones... 

Nickel carbonyl effects coupling of allylic halides when the reaction is carried out in very polar solvents such as DMF or DMSO. This coupling reaction has been used intramolecularly to bring about cyclization of to-allylic halides and was found useful in the preparation of large rings. 

The development of the Grignard-type addition to carbonyl compounds mediated by transition metals would be of interest as the compatibility with a variety of functionality would be expected under the reaction conditions employed. One example has been reported on the addition of allyl halides to aldehydes in the presence of cobalt or nickel metal however, yields were low (up to 22%). Benzylic nickel halides prepared in situ by the oxidative addition of benzyl halides to metallic nickel were found to add to benzil and give the corresponding 3-hydroxyketones in high yields(46). The reaction appears to be quite general and will tolerate a wide range of functionality. 

The first metal carbonyl prepared was Ni(CO)4, which was obtained by Mond in 1890. This extremely toxic compound was prepared by first reducing nickel oxide with hydrogen,... 

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). 

Preparation of a,(3- and p,y-unsaturated carboxylic acids using a nickel carbonyl complex... 

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). 

Caution Nickel carbonyl is a flammable, volatile b.p. 43°), highly toxic reagent. Safety glasses, gloves, and an apron should be worn when handling this reagent and the first step of this preparation should be conducted in an efficient hood (Note 1). 

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]. 

It has been claimed that attempts to prepare iron and nickel carbonyl complexes of 1,2-and 1,4-dihydropyridines resulted in reduction of the metal (67AG(E)988). This problem has been avoided by using dihydropyridines with electron withdrawing groups on the nitrogen... 

The deep-red, crystalline compound Ci0H14Ni, prepared by treating nickel carbonyl with cyclopentadienc, was first thought to have the structure dicyclopentadienenickel(O) [Ni(C6H6)2] (87). This compound has now been shown by nmr spectroscopy to have the structure T-cyclopentadienyl-7r-cyclopentenylnickel(II) (XLV), [Ni(7r-C5H6)(71--C6H7)] (70, 89,129). This... 

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

The method described is a modification of that of Gatter-mann and Koch.1 The aldehyde has also been prepared by related methods such as the action of hydrogen cyanide and hydrogen chloride on toluene in the presence of aluminum chloride,2 and nickel carbonyl with toluene and aluminum chloride.3 The reduction of />tolunitiile by stannous chloride forms the aldimine which on hydrolysis gives an almost quantitative yield of the aldehyde.4 />-Xylene can be oxidized by various reagents, particularly chromyl chloride,5 to />-tolualdehyde. 

Trimethylbenzaldehyde has been prepared from mes-itylglyoxylic acid,3,4 from mesitylene, nickel carbonyl, and aluminum chloride, and in excellent yield from mesitylene, hydrogen cyanide, and hydrogen chloride, as well as from mesitylene, carbon dioxide, and hydrogen chloride, in the presence of aluminum and cuprous chlorides.6 The above method is that applied to the preparation of other aldehydes by Rosen-mund and Zetzsche.7... 

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. 

Acrylic acid (CH2=CHC02H, melting point 13.5°C, boiling point 141°C, density 1.045, flash point 68°C) and acrylates were once prepared by reaction of acetylene and carbon monoxide with water or an alcohol, with nickel carbonyl as catalyst. 

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