13463-39-3 Usage
Uses
1. Nickel carbonyl is used as a purification intermediate in the refining of nickel.
2. It serves as a catalyst in the petroleum, plastic, and rubber industries.
3. Nickel carbonyl is used in the metallurgical and electronics industry for nickel vapor plating processes on steel and other metals.
4. It is utilized in the catalytic methyland ethylacrylate monomer synthesis.
5. For many years, it was used to produce pure nickel by the Mond process, which has been considered outdated since around 1970.
6. Nickel tetracarbonyl is used in the manufacture of nickel powder and nickel-coated metals, as well as a catalyst in carboxylation, coupling, and cyclization reactions.
7. In organic synthesis, it is used for the production of high-purity nickel powder and continuous nickel coatings on steel and other metals.
Physical Properties:
Colorless volatile liquid
Diamagnetic
Flammable
Burns with a bright luminous flame
Density: 1.319 g/mL
Freezes at -25°C
Boils at 43°C
Vapor pressure: 320.6 torr at 20°C
Vapor density: 5.89 (air=1)
Critical temperature: about 200°C
Critical pressure: 30 atm
Practically insoluble in water, 180 mg/L at 10°C
Miscible with most organic solvents, including ethanol, acetone, and benzene
Soluble in nitric acid and aqua regia
Chemical Properties:
Colorless liquid with a musty odor
Decomposes above room temperature, producing carbon monoxide and finely divided nickel
Used in the Metallurgical Industry:
Nickel carbonyl is used as a catalyst for nickel vapor plating processes on steel and other metals, enhancing the properties of the coated materials.
Used in the Electronics Industry:
Nickel carbonyl is employed in the production of high-purity nickel powder and continuous nickel coatings on steel and other metals, which are essential for various electronic components and devices.
Used in the Chemical Industry:
Nickel carbonyl is used as a catalyst in carboxylation, coupling, and cyclization reactions, playing a crucial role in the synthesis of various organic compounds.
Used in the Production of Nickel Powder and Coated Metals:
Nickel carbonyl is utilized in the manufacture of nickel powder and nickel-coated metals, which find applications in various industrial and commercial products.
History
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.
Production Methods
Nickel carbonyl is produced in a reaction of carbon monoxide
and nickel metal. It may also be formed as a by-product in
the industrial processes using nickel catalysts, such as coal
gasification, crude oil refining, and hydrogenation reactions
(293). Conditions for its formation occur in those
processes where carbon monoxide is in contact with an
active form of nickel under conditions of elevated pressure
at 50–150°C.
Preparation
Nickel tetracarbonyl is made by passing carbon monoxide over finely divided nickel at 50 to 100°C. (The finely divided nickel is obtained from reduction of nickel oxide by hydrogen below 400°C.) Ni + 4CO → Ni(CO)4In several commercial processes the reaction is carried out at a temperature of 200°C under 400 atm carbon monoxide pressure for obtaining high yield of nickel tetracarbonyl and also to prevent thermal dissociation.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, (C6H5—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: 2NiII + 4CO → NiIV(complex) + Nio(CO)4.
Air & Water Reactions
Highly flammable over a wide range of vapor-air concentrations. Is peroxidized by air to give a solid deposit that tends to decompose and ignite. Insoluble in water.
Reactivity Profile
NICKEL CARBONYL is easily oxidized. Presents a very serious fire hazard if exposed to heat, flame, sparks, oxidizing agents. Explodes when heated to about 60°C. Reacts explosively with bromine (liquid), oxygen in the presence of mercury, or hydrocarbons (butane) mixed with oxygen. Undergoes violent reactions with air, oxygen, dinitrogen tetraoxide. Caused an explosion when added to an n-butane-oxygen at 20-40°C [J. Am. Chem. Soc. 70:2055-6. 1948]. Reacts with tetrachloropropadiene to form an extremely explosive dinickel chloride dimer. Emits highly toxic fumes of carbon monoxide when heated to decomposition or in contact with mineral acids or acid fumes [Bretherick, 5th ed., 1995, p. 1734]. Vapor explodes in air or oxygen at 20°C and a partial pressure of 15 mm.
Hazard
Flammable, dangerous fire risk, explodes
at 60C (140F). A lung irritant and confirmed carcinogen.
Health Hazard
Probable oral lethal dose for a human is between 50 and 500 mg/kg, between one teaspoon and one ounce per 150 lb. person. NICKEL CARBONYL has also been estimated to be lethal in man at atmospheric exposures of 30 ppm for 20 minutes. Autopsies show congestion, collapse, and tissue destruction, as well as hemorrhage in the brain. Dermatitis, recurrent asthmatic attacks, and increased number of white blood cells (eosinophils) in respiratory tract are acute health hazards. NICKEL CARBONYL is poisonous. It can be fatal if inhaled, swallowed, or absorbed through skin. Vapors may cause irritation, congestion, and edema of lungs.
Health Hazard
The acute toxicity of nickel carbonyl by inhalation is high. Acute toxic effects occur
in two stages, immediate and delayed. Headache, dizziness, shortness of breath,
vomiting, and nausea are the initial symptoms of overexposure; the delayed effects
(10 to 36 h) consist of chest pain, coughing, shortness of breath, bluish discoloration
of the skin, and in severe cases, delirium, convulsions, and death. Recovery is
protracted and characterized by fatigue on slight exertion. Nickel carbonyl is not
regarded as having adequate warning properties.
Repeated or prolonged exposure to nickel carbonyl has been associated with an
increased incidence of cancer of the lungs and sinuses. Nickel carbonyl is listed by
IARC in Group 2B ("possible human carcinogen"), is listed by NTP as "reasonably
anticipated to be a carcinogen," and is classified as a "select carcinogen'' under the
criteria of the OSHA Laboratory Standard.
Health Hazard
Nickel tetracarbonyl is an extremely toxicsubstance by all routes of exposure exhibitingboth immediate and delayed effects. Thedelayed effects may manifest in a few hoursto days after exposure. Exposure to its vaporscan cause dizziness, giddiness, headache,weakness, and increased body temperature.Vapors are irritating to eyes, nose, andthroat. Prolonged exposure or inhalation ofits vapors at a further increased level ofconcentration may produce rapid breathing,followed by congestion of the lungs. Therespiration will initially be rapid with nonproductivecough, progressing to pain andtightness in the chest (U.S. EPA 1995). Highexposure can cause convulsion, hemorrhage,and death. Other symptoms from inhalationof vapors or ingestion of the liquid includehallucinations, delirium, nausea, vomiting,diarrhea, and liver and brain injury. In humans, a 30-minute exposure to a 30-ppm concentration in air could be fatal. Afew whiffs of the vapors of the liquid cancause death. One minute exposure to 3000ppm of its vapor can cause death in humansfrom respiratory failure and acute pulmonaryedema. Similarly, swallowing 5–10 mL ofthe liquid can be fatal. Nickel tetracarbonyl can be absorbedthrough the skin. While the skin contact witha dilute solution can cause dermatitis anditching, that from a concentrated solution orthe pure liquid can produce a burn. Absorptionof the liquid through the skin may resultin death. The subcutaneous and intravenousLD50 values in rats are 60–70 mg/kg. LC50 (mouse): 0.067 mg/L/30 min (RTECS2004) Evidence of carcinogenicity observed inexperimental animals dosed with nickel tetracarbonyl is limited. It caused tumors inthe lungs and liver. The compound is alsoteratogenic, causing birth defects.
Fire Hazard
Nickel carbonyl is a highly flammable liquid (NFPA rating = 3) that may ignite
spontaneously and explodes when heated above 60℃. Its lower flammable limit in
air is 2% by volume; the upper limit has not been reported. Carbon dioxide, water, or
dry chemical extinguishers should be used for nickel carbonyl fires.
Fire Hazard
Vapor forms explosive mixtures with air. Vapor is heavier than air and may travel a considerable distance to source of ignition and flash back. Liquid may explode when heated under confinement. Vapor explosion and poison hazard indoors, outdoors, or in sewers. Runoff to sewer may create fire and explosion. May explode at 68F in presence of air or oxygen. Avoid contact with heat, acid or acid fumes as these cause the emission of highly toxic fumes. Avoid contact with air, ignition sources and vapors entering a confined space.
Flammability and Explosibility
Nickel carbonyl is a highly flammable liquid (NFPA rating = 3) that may ignite
spontaneously and explodes when heated above 60 °C. Its lower flammable limit in
air is 2% by volume; the upper limit has not been reported. Carbon dioxide, water, or
dry chemical extinguishers should be used for nickel carbonyl fires.
Safety Profile
ConfEmed carcinogen
with experimental carcinogenic,
tumorigenic, and teratogenic data. A human
poison by inhalation. Poison experimentally
by inhalation, intravenous, subcutaneous,
and intraperitoneal routes. An experimental
teratogen. Other experimental reproductive
effects. Human systemic effects by
inhalation: somnolence, fever, and other
pulmonary changes. Vapors may cause
coughing, dyspnea (difficult breathing),
irritation, congestion and edema of the
lungs, tachycardia (rapid pulse), cyanosis,
headache, dizziness, and weakness. Toxicity
by inhalation is believed to be caused by
both the nickel and carbon monoxide
liberated in the lungs. Chronic exposure may
cause cancer of lungs, nasal sinuses.
Sensitization dermatitis is fairly common.
Probably the most hazardous compound of
nickel in the workplace. A common air
contaminant. It is lipid soluble and can cross
biological membranes (e.g., lung alveolus,
blood-brain barrier, placental barrier).
A very dangerous fire hazard when
exposed to heat, flame, or oxidizers.
Moderate explosion hazard when exposed
to heat or flame. Explodes when heated to
about 60°. Explosive reaction with liquid
bromine, mercury + oxygen, oxygen +
butane. Violent reaction with dinitrogen
tetraoxide, air, oxygen. Reacts with
tetrachloropropadtene to form the extremely
sensitive explosive dicarbonyl
trichloropropenyl dinickel chloride dimer.
Can react with oxidzing materials. To fight
fire, use water, foam, CO2, dry chemical.
When heated to decomposition or on
contact with acid or acid fumes, it emits
highly toxic fumes of carbon monoxide. See
also NICKEL COMPOUNDS and
CARBONYLS.
Potential Exposure
Nickel carbonyl is used as an intermediate
product in the refining of nickel. The primary use for
nickel carbonyl is in the production of nickel by the Mond
process. Impure nickel powder is reacted with carbon monoxide
to form gaseous nickel carbonyl which is then treated
to deposit high purity metallic nickel and release carbon
monoxide. Other uses include gas plating; the production
of nickel products; in chemical synthesis as a catalyst, particularly
for oxo reactions (addition reaction of hydrogen
and carbon monoxide with unsaturated hydrocarbons to
form oxygen-function compounds); e.g., synthesis of
acrylic esters; and as a reactant.
storage
Work with nickel
carbonyl should be conducted in a fume hood to prevent exposure by inhalation and
splash goggles and impermeable gloves should be worn at all times to prevent eye
and skin contact. Nickel carbonyl should only be used in areas free of ignition
sources. Containers of nickel carbonyl should be stored in secondary containers in
the dark in areas separate from oxidizers.
Shipping
UN1259 Nickel carbonyl, Hazard Class: 6.1;
Labels: 6.1-Poisonous materials, 3-Flammable liquid,
Inhalation Hazard Zone A. A United States DOT Severe
Marine Pollutant.
Incompatibilities
May spontaneously ignite on contact
with air. In the presence of air, oxidizes and forms a
deposit which becomes peroxidized; this tends to decompose
and ignite. May explode when heated above 60 C.
Decomposes on contact with acids producing carbon monoxide.
Violent reaction with oxidizers; may cause fire and
explosions. Vapor may promote the ignition of mixtures of
combustible vapors (such as gasoline) and air. Attacks
some plastics, rubber and coatings. Store under inert gas
blanket.
Waste Disposal
Incineration in admixture
with a flammable solvent. Also, nickel carbonyl used in
metallizing operations may be recovered and recycled.
Consult with environmental regulatory agencies for guidance
on acceptable disposal practices. Generators of waste
containing this contaminant (≥100 kg/mo) must conform
with EPA regulations governing storage, transportation,
treatment, and waste disposal.
Check Digit Verification of cas no
The CAS Registry Mumber 13463-39-3 includes 8 digits separated into 3 groups by hyphens. The first part of the number,starting from the left, has 5 digits, 1,3,4,6 and 3 respectively; the second part has 2 digits, 3 and 9 respectively.
Calculate Digit Verification of CAS Registry Number 13463-39:
(7*1)+(6*3)+(5*4)+(4*6)+(3*3)+(2*3)+(1*9)=93
93 % 10 = 3
So 13463-39-3 is a valid CAS Registry Number.
InChI:InChI=1/4CO.Ni/c4*1-2;/rC4NiO4/c6-1-5(2-7,3-8)4-9
13463-39-3Relevant articles and documents
Icosahedral Ga-centred nickel carbonyl clusters: Synthesis and characterization of [H3-nNi12 (μ12-Ga)(CO) 22]n- (n = 2, 3) and [Ni14.3(μ12- Ga)(CO)24.3]3- anions
Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Zacchini, Stefano
, p. 1056 - 1062 (2010)
The reaction of [Ni5(CO)12]2- or [Ni 6(CO)12]2- with GaCl3 in dichloromethane under a nitrogen atmosphere affords a mixture of [Ni 12+x(μ12-Ga)(CO)22+x]3- (x = 0-3) clusters. Short exposure of the above mixture to a carbon monoxide atmosphere leads to the green icosahedral [Ni12(μ12-Ga)(CO) 22]3- trianion, which was isolated and characterized as its [NnBu4]+ salt. In contrast, crystallization of the above mixture in the presence of Ni(CO)4 enabled isolation of a cocrystallized mixture of [Ni14(μ12-Ga)(CO) 24]3- (70%) and [Ni15(μ12-Ga)(CO) 25]3- (30%). As inferable from its structure, the additional three Ni(CO) moieties condense onto interlayer faces of the icosahedron. Protonation of [Ni12(μ12-Ga)-(CO) 22]3- affords the corresponding [HNi12(μ 12-Ga)(CO)22]2- hydride derivative, which was isolated in a pure state and fully characterized. All of the above compounds conform to the cluster-borane analogy, by the inclusion principle, and none exhibits relevant redox behaviour.
Generation of a Ni3Phosphinidene Cluster from the Ni(0) Synthon, Ni(η3-CPh3)2
Touchton, Alexander J.,Wu, Guang,Hayton, Trevor W.
, p. 1360 - 1365 (2020)
Reaction of NiCl2 in THF with 2 equiv of Li(CPh3) at -25 °C results in formation of Ni(η3-CPh3)2 (1) in moderate yield. Complex 1 was fully characterized, which included analysis by X-ray crystallography. In the solid state, 1 features an η3 binding mode
Molecular nickel poly-carbide carbonyl nanoclusters: The octa-carbide [HNi42C8(CO)44(CuCl)]7- and the deca-carbide [Ni45C10(CO)46]6-
Bernardi, Alessandro,Ciabatti, Iacopo,Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Zacchini, Stefano
, p. 229 - 239 (2016)
The reaction of [Ni10(C2) (CO)16]2- with CuCl in thf affords [Ni45C10(CO)46]6- as the major product. This represents the first deca-carbide carbonyl cluster and this i
Cadmium-substitution promoted by nucleophilic attack of [Ni30C4(CO)34(CdX)2]6- (X = Cl, Br, I) carbido carbonyl clusters: Synthesis and characterization of the new [H7-nNi32C
Bernardi, Alessandro,Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Zacchini, Stefano
, p. 1239 - 1246 (2009)
The reaction of [Ni9C(CO)17]2- with CdX2 · xH2O (X = Cl, Br, I) affords the tetra-carbide carbonyl clusters [H6-nNi30C4(CO)34(CdX)2]n-
Hetero-bimetallic Ni-Rh carbido carbonyl clusters: Synthesis, structure and13C NMR of [Ni10Rh2C(CO)2O] 2-, [Ni9Rh3C(CO)20]3- and [Ni6Rh8
Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Zacchini, Stefano
, p. 2487 - 2495 (2009)
The reaction of [Ni8C(CO)I7]2- (1) with [Rh(cod)Cl]2 (2) results in the formation of the new hetero-bimetallic [Ni10Rh2C(CO)20]2 (3) and [Ni9Rh3C
A study of Cu/ZnO/Al2O3 methanol catalysts prepared by flame combustion synthesis
Jensen,Johannessen,Wedel,Livbjerg
, p. 67 - 77 (2003)
The flame combustion synthesis of Cu/ZnO/Al2O3 catalysts for the synthesis of methanol from CO, CO2, and H2 was studied. A low peak temperature and quench cooling of the flame tended to increase the dispersion of the phases and the specific surface area of the particles. The specific surface area varied from ≤ 100 sq m/g for samples without aluminum to several hundred square m per gram for the respective compositions of pure Al2O3 and ZnAl2O4. The samples prepared and tested with copper as one of the components showed potential for use as methanol catalysts. The contribution of ZnAl2O4 to an increased surface area and thermal stability was the explanation of the beneficial role of alumina in the methanol synthesis catalyst. Although Cu/Al2O3 showed methanol synthesis activity, the Cu-based turnover frequency was inferior to that of the ZnO-containing catalysts. Methane, which is the only detectable by-product of the reaction, was produced in minute amounts unless the catalyst was contaminated by nickel.
Steric and electronic properties of N-heterocyclic carbenes (NHC): A detailed study on their interaction with Ni(CO)4
Dorta, Reto,Scott, Natalie M.,Costabile, Chiara,Cavallo, Luigi,Hoff, Carl D.,Nolan, Steven P.
, p. 2485 - 2495 (2005)
N-heterocyclic carbene ligands IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5) react with Ni(CO)4 to give the saturated tricarbonyl complexes Ni(CO)3(IMeS) (8), Ni(CO)3(SIMeS) (9), Ni(CO)3(IPr) (10), Ni(CO)3(SIPr) (11), and Ni(CO) 3(ICy) (12), respectively. The electronic properties of these complexes have been compared to their phosphine analogues of general formula Ni(CO)3(PR3) by recording their vco stretching frequencies. While all of these NHCs are better donors than tertiary phosphines, the differences in donor properties between ligands 1-5 are surprisingly small. Novel, unsaturated Ni(CO)2(IAd) (13) and Ni(CO)2(I tBu) (14) compounds are obtained from the reaction of Ni(CO) 4 with IAd (6) and ItBu (7). Complexes 13 and 14 are highly active toward substitution of the NHC as well as the carbonyl ligands. This has allowed the determination of Ni-C(NHC) bond dissociation energies and the synthesis of various unsaturated Ni(0) and Ni(II) complexes. Computational studies on compounds 8-14 are in line with the experimental findings and show that IAd (6) and ItBu (7) are more bulky than IMes (1), SIMes (2), IPr (3), SIPr (4), and ICy (5). Furthermore, a method based on % Vbur values has been developed for the direct comparison of steric requirements of NHCs and tertiary phosphines. Complexes 8-14, as well as NiCl(C 3H5)(ItBu) (16) and NiBr(C3H 5)(ItBu) (17), have been characterized by X-ray crystallography.
Paramagnetic nickel(I) complexes and their role in the catalytic dimerization of norbornadiene
Otman,Manulik,Flid
, p. 479 - 483 (2008)
The kinetics of the formation of a paramagnetic nickel(I) complex from bis(η3-allyl)nickel under conditions of catalytic norbornadiene dimerization is reported. It is demonstrated by ESR and GLC that the concentrations of Ni(I), norbornadiene and its pentacyclic dimers change in the same way. It might be inferred from this finding that Ni(I) is involved in the catalytic process as an intermediate. However, experiments on model systems have not confirmed this assumption. At the same time, they have not ruled out the participation of the paramagnetic complex in side catalytic reactions. The presence of Ni(I) in the reaction system is connected with the presence of free norbornadiene there. Hypotheses as to the probable structure and formation mechanism of the paramagnetic Ni(I) are suggested.
A highly active Ni/ZSM-5 catalyst for complete hydrogenation of polymethylbenzenes
Qi, Shi-Chao,Wei, Xian-Yong,Zong, Zhi-Min,Hayashi, Jun-Ichiro,Yuan, Xin-Hua,Sun, Lin-Bing
, p. 3543 - 3547 (2013)
Amazing the crowd: A highly dispersive supported nickel catalyst is prepared by in situ decomposition of Ni(CO)4 over ZSM-5 zeolite. The catalyst displays an amazing activity for complete hydrogenation of polymethylbenzenes which are extremely
Condensation of nickel-carbonyl clusters with soft lewis acids: Synthesis and characterisation of the {Cd2Cl3[Ni6(CO) 12]2}3- dimer
Femoni, Cristina,Iapalucci, Maria Carmela,Longoni, Giuliano,Ranuzzi, Fabrizio,Zacchini, Stefano,Fedi, Serena,Zanello, Piero
, p. 4064 - 4070 (2007)
Reaction of [Ni6(CO)12]2- in thf with 2 equiv. of the soft Lewis acid CdCl2·2.5H2O gives the new dimeric species {Cd2Cl3[Ni6(CO) 12]2}3-/su
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