Nickel carbonyl, effect

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. 

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). 

Nickel carbonyl is volatile, has Htde odor, and is extremely toxic. Symptoms of dangerous exposure may not appear for several days. Effective medical treatment should be started immediately. The plant should be designed to ensure containment of nickel carbonyl and to prevent operator contact. 

It is good practice to keep concentrations of airborne nickel in any chemical form as low as possible and certainly below the relevant standard. Local exhaust ventilation is the preferred method, particularly for powders, but personal respirator protection may be employed where necessary. In the United States, the Occupational Safety and Health Administration (OSHA) personal exposure limit (PEL) for all forms of nickel except nickel carbonyl is 1 mg/m. The ACGIH TLVs are respectively 1 mg/m for Ni metal, insoluble compounds, and fume and dust from nickel sulfide roasting, and 0.1 mg/m for soluble nickel compounds. The ACGIH is considering whether to lower the TLVs for all forms of nickel to 0.05 mg/m, based on nonmalignant respiratory effects in experimental animals. 

Nickel carbonyl is an extremely toxic substance, but a number of other nickel reagents with generally similar reactivity can be used in its place. The Ni(0) complex of 1,5-cyclooctadiene, Ni(COD)2, can effect coupling of allylic, alkenyl, and aryl halides. 

The second approach consists of synthesizing first the complex MLra 1(L X) with the desired ratio (L )/(M) this complex bears the reactive fragment X which then reacts with the surface of the silica. This method is of limited interest, because the synthesis and isolation of these functionalized complexes is not straightforward. One of the successful examples concerns the synthesis of nickel carbonyl complexes anchored to the surface via two bonds in an attempt to increase the stability through a sort of chelate effect. Initial attempts to achieve this by the methods described in Equation(5) (initial functionalization of silica) and Equation(6) (initial functionalization of complex) failed, as demonstrated by 29Si and 31P CP MAS NMR spectroscopies.51... 

Inhalation of nickel compounds other than nickel carbonyl causes significant effects in humans, rats, mice, rabbits, and dogs, with respiratory effects being most common. 

To protect humans and other mammals, proposed air-quality criteria range from 0.01 to less than 1.0 mg/m3 for metallic nickel and slightly soluble nickel compounds, 0.015-0.5 mg/m3 for water soluble nickel compounds, and 0.005 to 0.7 mg/m3 for nickel carbonyl (Table 6.10). Inhalation of nickel subsulfide concentrations (0.11 to 1.8 mg Ni/m3) near the current threshold limit value of 1 mg Ni/m3 can produce detrimental changes in the respiratory tract of rats after only a few days of exposure (Benson et al. 1995). Additional animal studies are recommended to identify minimally effective inhalation exposure levels for the various nickel compounds (USPHS 1993). Continued monitoring of nickel refining, nickel-cadmium battery manufacture, and nickel powder metallurgy installations is recommended because ambient air levels of bioavailable nickel at these... 

By analogy to nickel carbonyl, acute effects from animal exposures are expected to be pulmonary edema, congestion, and hemorrhage. In humans, nickel carbonyl causes an acute flulike syndrome that subsides and is followed after 12-36 hours by an acute respiratory syndrome. Exposure to cobalt hydrocarbonyl may be expected to produce similar effects. 

Iron pentacarbonyl is approximately one-third as potent as nickel carbonyl when inhaled by rats for 30 minutes. Effects from inhalation of high concentrations of the chemical are expected to be similar to those of nickel carbonyl, which include frontal headache, vertigo, nausea, vomiting, and sometimes substernal and epigastric pain. Generally these early effects disappear when the subject is removed to fresh air. 

In rodent studies iron pentacarbonyl was found to have approximately one-third the acute toxicity of nickel carbonyl. At 33 ppm for 5.5 hours three of eight rats died at 18 ppm four of eight died after two 5.5-hour exposures. Multiple 5.5-hour exposures at 7ppm caused no apparent effects. 

The severe acute systemic effects found with nickel carbonyl exposure are not associated with inorganic nickel. ... 

In the case of phosphine, especially tri-n-butyl and triphenyl phosphines, an active phosphine complex is formed in the reaction medium via reaction with nickel carbonyl. This complex is a very active species provided that the optimum concentration of phosphine is used. Low phosphine concentration results in a loss of the effective nickel concentration through the formation of nickel tetra-carbonyl, nickel metal or nickel iodide. The absolute concentration of phosphine is less important than the P/Ni ratio. In addition to form the stable Ni-P catalyst, the phosphine has to compete with other ligands in the reaction mixture for nickel. With high carbon monoxide partial pressure, there is more CO in solution to compete with phosphine favoring the formation of the carbonyl, which is inactive under the reaction conditions. Hence with high carbon mon-... 

Carbonylation of methanol to form acetic acid has been performed industrially using carbonyl complexes of cobalt ( ) or rhodium (2 ) and iodide promoter in the liquid phase. Recently, it has been claimed that nickel carbonyl or other nickel compounds are effective catalysts for the reaction at pressure as low as 30 atm (2/4), For the rhodium catalyst, the conditions are fairly mild (175 C and 28 atm) and the product selectivity is excellent (99% based on methanol). However, the process has the disadvantages that the proven reserves of rhodium are quite limited in both location and quantity and that the reaction medium is highly corrosive. It is highly desirable, therefore, to develop a vapor phase process, which is free from the corrosion problem, utilizing a base metal catalyst. The authors have already reported that nickel on activated carbon exhibits excellent catalytic activity for the carbonylation of... 

Investigations showed that the salts of other alkali metals are not so efficient in suppressing secondary flame as potassium salts. Fairly numerous experiments were carried out to clear up whether or not known antiknock substances, such as tetraethyl lead or nickel carbonyl prevent the development of a secondary flame. They proved to have no effect on its development. In practice, two methods for removing gun-flash may be employed, i.e. either a special flashless powder is produced, containing nitroguanidine or DNT and a small admixture of potassium sulphate,... 

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