Nickel tetracarbonyl

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Nickel tetracarbonyl
Nickel-tetracarbonyl-2D.png
Nickel carbonyl Nickel-tetracarbonyl-3D-balls.png
Nickel carbonyl
Nickel carbonyl Nickel-carbonyl-3D-vdW.png
Nickel carbonyl
Names
IUPAC name
Tetracarbonylnickel
Other names
Nickel tetracarbonyl
Nickel carbonyl (1:4)
Identifiers
3D model (JSmol)
6122797
ChEBI
ChemSpider
ECHA InfoCard 100.033.322 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 236-669-2
3135
PubChem CID
RTECS number
  • QR6300000
UNII
UN number 1259
  • InChI=1S/4CO.Ni/c4*1-2; Yes check.svgY
    Key: AWDHUGLHGCVIEG-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/4CO.Ni/c4*1-2;/rC4NiO4/c6-1-5(2-7,3-8)4-9
    Key: AWDHUGLHGCVIEG-ARWXMKMZAJ
  • [O+]#C[Ni-4](C#[O+])(C#[O+])C#[O+]
Properties
Ni(CO)4
Molar mass 170.73 g/mol
Appearancecolorless liquid [1]
Odor musty, [1] like brick dust
Density 1.319 g/cm3
Melting point −17.2 °C (1.0 °F; 256.0 K)
Boiling point 43 °C (109 °F; 316 K)
0.018 g/100 mL (10 °C)
Solubility miscible in most organic solvents
soluble in nitric acid, aqua regia
Vapor pressure 315 mmHg (20 °C) [1]
Viscosity 3.05 x 10−4 Pa s
Structure
Tetrahedral
Tetrahedral
zero
Thermochemistry
Std molar
entropy
(S298)
320 JK−1mol−1
−632 kJ/mol
−1180 kJ/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
Potential occupational carcinogen [2]
GHS labelling:
GHS-pictogram-skull.svg GHS-pictogram-silhouette.svg GHS-pictogram-flamme.svg GHS-pictogram-pollu.svg
H225, H300, H301, H304, H310, H330, H351, H360D, H410
P201, P202, P210, P233, P240, P241, P242, P243, P260, P271, P273, P280, P281, P284, P303+P361+P353, P304+P340, P308+P313, P310, P320, P370+P378, P391, P403+P233, P403+P235, P405, P501
NFPA 704 (fire diamond)
NFPA 704.svgHealth 4: Very short exposure could cause death or major residual injury. E.g. VX gasFlammability 3: Liquids and solids that can be ignited under almost all ambient temperature conditions. Flash point between 23 and 38 °C (73 and 100 °F). E.g. gasolineInstability 3: Capable of detonation or explosive decomposition but requires a strong initiating source, must be heated under confinement before initiation, reacts explosively with water, or will detonate if severely shocked. E.g. hydrogen peroxideSpecial hazards (white): no code
4
3
3
Flash point 4 °C (39 °F; 277 K)
60 °C (140 °F; 333 K)
Explosive limits 2–34%
Lethal dose or concentration (LD, LC):
266 ppm (cat, 30 min)
35 ppm (rabbit, 30 min)
94 ppm (mouse, 30 min)
10 ppm (mouse, 10 min) [3]
360 ppm (dog, 90 min)
30 ppm (human, 30 min)
42 ppm (rabbit, 30 min)
7 ppm (mouse, 30 min) [3]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 0.001 ppm (0.007 mg/m3) [1]
REL (Recommended)
TWA 0.001 ppm (0.007 mg/m3) [1]
IDLH (Immediate danger)
Ca [2 ppm] [1]
Safety data sheet (SDS) ICSC 0064
Related compounds
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Nickel carbonyl (IUPAC name: tetracarbonylnickel) is a nickel(0) organometallic compound with the formula Ni(CO)4. This colorless liquid is the principal carbonyl of nickel. It is an intermediate in the Mond process for producing very high-purity nickel and a reagent in organometallic chemistry, although the Mond Process has fallen out of common usage due to the health hazards in working with the compound. Nickel carbonyl is one of the most dangerous substances yet encountered in nickel chemistry due to its very high toxicity, compounded with high volatility and rapid skin absorption. [4]

Contents

Structure and bonding

In nickel tetracarbonyl, the oxidation state for nickel is assigned as zero, because the Ni-C bonding electrons come from the C atom and are still assigned to C in the hypothetical ionic bond which determines the oxidation states. The formula conforms to the 18-electron rule. The molecule is tetrahedral, with four carbonyl (carbon monoxide) ligands. Electron diffraction studies have been performed on this molecule, and the Ni–C and C–O distances have been calculated to be 1.838(2) and 1.141(2) angstroms respectively. [5]

Preparation

Ni(CO)4 was first synthesised in 1890 by Ludwig Mond by the direct reaction of nickel metal with carbon monoxide. [6] This pioneering work foreshadowed the existence of many other metal carbonyl compounds, including those of vanadium, chromium, manganese, iron, and cobalt. It was also applied industrially to the purification of nickel by the end of the 19th century. [7]

At 323 K (50 °C; 122 °F), carbon monoxide is passed over impure nickel. The optimal rate occurs at 130 °C. [8]

Laboratory routes

Ni(CO)4 is not readily available commercially. It is conveniently generated in the laboratory by carbonylation of commercially available bis(cyclooctadiene)nickel(0). [9] It can also be prepared by reduction of ammoniacal solutions of nickel sulfate with sodium dithionite under an atmosphere of CO. [10]

Reactions

Spheres of nickel made by the Mond process Nickel kugeln.jpg
Spheres of nickel made by the Mond process

Thermal decarbonylation

On moderate heating, Ni(CO)4 decomposes to carbon monoxide and nickel metal. Combined with the easy formation from CO and even very impure nickel, this decomposition is the basis for the Mond process for the purification of nickel or plating onto surfaces. Thermal decomposition commences near 180 °C (356 °F) and increases at higher temperature. [8]

Reactions with nucleophiles and reducing agents

Like other low-valent metal carbonyls, Ni(CO)4 is susceptible to attack by nucleophiles. Attack can occur at nickel center, resulting in displacement of CO ligands, or at CO. Thus, donor ligands such as triphenylphosphine react to give Ni(CO)3(PPh3) and Ni(CO)2(PPh3)2. Bipyridine and related ligands behave similarly. [11] The monosubstitution of nickel tetracarbonyl with other ligands can be used to determine the Tolman electronic parameter, a measure of the electron donating or withdrawing ability of a given ligand.

Structure of Ni(PPh3)2(CO)2. NiP2(CO)2.svg
Structure of Ni(PPh3)2(CO)2.

Treatment with hydroxides gives clusters such as [Ni5(CO)12]2− and [Ni6(CO)12]2−. These compounds can also be obtained by reduction of nickel carbonyl.

Thus, treatment of Ni(CO)4 with carbon nucleophiles (Nu) results in acyl derivatives such as [Ni(CO)3C(O)Nu)]. [12]

Reactions with electrophiles and oxidizing agents

Nickel carbonyl can be oxidized. Chlorine oxidizes nickel carbonyl into NiCl2, releasing CO gas. Other halogens behave analogously. This reaction provides a convenient method for precipitating the nickel portion of the toxic compound.

Reactions of Ni(CO)4 with alkyl and aryl halides often result in carbonylated organic products. Vinylic halides, such as PhCH=CHBr, are converted to the unsaturated esters upon treatment with Ni(CO)4 followed by sodium methoxide. Such reactions also probably proceed via oxidative addition. Allylic halides give the π-allylnickel compounds, such as (allyl)2Ni2Cl2: [13] 2 Ni(CO)4 + 2 ClCH2CH=CH2 → Ni2 (μ-Cl)2(η3-C3H5)2 + 8 CO

Toxicology and safety considerations

The hazards of Ni(CO)4 are far greater than that implied by its CO content, reflecting the effects of the nickel if released in the body. Nickel carbonyl may be fatal if absorbed through the skin or more likely, inhaled due to its high volatility. Its LC50 for a 30-minute exposure has been estimated at 3  ppm, and the concentration that is immediately fatal to humans would be 30 ppm. Some subjects exposed to puffs up to 5 ppm described the odour as musty or sooty, but because the compound is so exceedingly toxic, its smell provides no reliable warning against a potentially fatal exposure. [14]

The vapours of Ni(CO)4 can autoignite. The vapor decomposes quickly in air, with a half-life of about 40 seconds. [15]

Nickel carbonyl poisoning is characterized by a two-stage illness. The first consists of headaches and chest pain lasting a few hours, usually followed by a short remission. The second phase is a chemical pneumonitis which starts after typically 16 hours with symptoms of cough, breathlessness and extreme fatigue. These reach greatest severity after four days, possibly resulting in death from cardiorespiratory or acute kidney injury. Convalescence is often extremely protracted, often complicated by exhaustion, depression and dyspnea on exertion. Permanent respiratory damage is unusual. The carcinogenicity of Ni(CO)4 is a matter of debate, but is presumed to be significant.

It is classified as an extremely hazardous substance in the United States as defined in Section 302 of the U.S. Emergency Planning and Community Right-to-Know Act (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities. [16]

"Requiem for the Living" (1978), an episode of Quincy, M.E. , features a poisoned, dying crime lord who asks Dr. Quincy to autopsy his still-living body. Quincy identifies the poison—nickel carbonyl.

In the 1979 novella Amanda Morgan by Gordon R. Dickson, the remaining inhabitants of a mostly evacuated village resist an occupying military force by directing the exhaust from a poorly-tuned internal combustion engine onto a continually renewed "waste heap" of powdered nickel outside a machine shop (under the guise of civilian business) in order to eliminate the occupiers, at the cost of their own lives.

In chapter 199 of the manga Dr. Stone , a machine is made that purifies nickel via the Mond Process. It is mentioned that the process creates a "fatal toxin" (nickel carbonyl).

In the 2019 novel Delta-v from New York Times bestselling author Daniel Suarez a team of eight private miners reach a near-earth asteroid to extract volatiles (water, CO2, etc.) and metals (iron, nickel and cobalt); these are stored as solid carbonyl for transfer back to near Earth orbit, and used for in-situ fabrication of a spacecraft, via decomposition in vacuum.

Related Research Articles

<span class="mw-page-title-main">Carbon monoxide</span> Colourless, odourless, tasteless and toxic gas

Carbon monoxide is a poisonous, flammable gas that is colorless, odorless, tasteless, and slightly less dense than air. Carbon monoxide consists of one carbon atom and one oxygen atom connected by a triple bond. It is the simplest carbon oxide. In coordination complexes, the carbon monoxide ligand is called carbonyl. It is a key ingredient in many processes in industrial chemistry.

<span class="mw-page-title-main">Nickel</span> Chemical element, symbol Ni and atomic number 28

Nickel is a chemical element; it has symbol Ni and atomic number 28. It is a silvery-white lustrous metal with a slight golden tinge. Nickel is a hard and ductile transition metal. Pure nickel is chemically reactive, but large pieces are slow to react with air under standard conditions because a passivation layer of nickel oxide forms on the surface that prevents further corrosion. Even so, pure native nickel is found in Earth's crust only in tiny amounts, usually in ultramafic rocks, and in the interiors of larger nickel–iron meteorites that were not exposed to oxygen when outside Earth's atmosphere.

<span class="mw-page-title-main">Organic compound</span> Chemical compound with carbon-hydrogen bonds

Some chemical authorities define an organic compound as a chemical compound that contains carbon–hydrogen or carbon–carbon bond; others consider an organic compound to be any chemical compound that contains carbon. For example, carbon-containing compounds such as alkanes and its derivatives are universally considered organic, but many others are sometimes considered inorganic, such as halides of carbon without carbon-hydrogen and carbon-carbon bonds, and certain compounds of carbon with nitrogen and oxygen.

<span class="mw-page-title-main">Organometallic chemistry</span> Study of organic compounds containing metal(s)

Organometallic chemistry is the study of organometallic compounds, chemical compounds containing at least one chemical bond between a carbon atom of an organic molecule and a metal, including alkali, alkaline earth, and transition metals, and sometimes broadened to include metalloids like boron, silicon, and selenium, as well. Aside from bonds to organyl fragments or molecules, bonds to 'inorganic' carbon, like carbon monoxide, cyanide, or carbide, are generally considered to be organometallic as well. Some related compounds such as transition metal hydrides and metal phosphine complexes are often included in discussions of organometallic compounds, though strictly speaking, they are not necessarily organometallic. The related but distinct term "metalorganic compound" refers to metal-containing compounds lacking direct metal-carbon bonds but which contain organic ligands. Metal β-diketonates, alkoxides, dialkylamides, and metal phosphine complexes are representative members of this class. The field of organometallic chemistry combines aspects of traditional inorganic and organic chemistry.

<span class="mw-page-title-main">Vaska's complex</span> Chemical compound

Vaska's complex is the trivial name for the chemical compound trans-carbonylchlorobis(triphenylphosphine)iridium(I), which has the formula IrCl(CO)[P(C6H5)3]2. This square planar diamagnetic organometallic complex consists of a central iridium atom bound to two mutually trans triphenylphosphine ligands, carbon monoxide and a chloride ion. The complex was first reported by J. W. DiLuzio and Lauri Vaska in 1961. Vaska's complex can undergo oxidative addition and is notable for its ability to bind to O2 reversibly. It is a bright yellow crystalline solid.

<span class="mw-page-title-main">Molybdenum hexacarbonyl</span> Chemical compound

Molybdenum hexacarbonyl (also called molybdenum carbonyl) is the chemical compound with the formula Mo(CO)6. This colorless solid, like its chromium, tungsten, and seaborgium analogues, is noteworthy as a volatile, air-stable derivative of a metal in its zero oxidation state.

<span class="mw-page-title-main">Iron pentacarbonyl</span> Chemical compound

Iron pentacarbonyl, also known as iron carbonyl, is the compound with formula Fe(CO)5. Under standard conditions Fe(CO)5 is a free-flowing, straw-colored liquid with a pungent odour. Older samples appear darker. This compound is a common precursor to diverse iron compounds, including many that are useful in small scale organic synthesis.

<span class="mw-page-title-main">Chromium hexacarbonyl</span> Chemical compound

Chromium hexacarbonyl is a chromium(0) organometallic compound with the formula Cr(CO)6. It is a homoleptic complex, which means that all the ligands are identical. It is a colorless crystalline air-stable solid, with a high vapor pressure.

<span class="mw-page-title-main">Metal carbonyl</span> Coordination complexes of transition metals with carbon monoxide ligands

Metal carbonyls are coordination complexes of transition metals with carbon monoxide ligands. Metal carbonyls are useful in organic synthesis and as catalysts or catalyst precursors in homogeneous catalysis, such as hydroformylation and Reppe chemistry. In the Mond process, nickel tetracarbonyl is used to produce pure nickel. In organometallic chemistry, metal carbonyls serve as precursors for the preparation of other organometallic complexes.

<span class="mw-page-title-main">Mond process</span> Process to extract and purify nickel

The Mond process, sometimes known as the carbonyl process, is a technique created by Ludwig Mond in 1890, to extract and purify nickel. The process was used commercially before the end of the 19th century, and particularly by the International Nickel Company in the Sudbury Basin. This process converts nickel oxides into nickel metal with very high purity being attainable in just a single step.

Carbonyl fluoride is a chemical compound with the formula COF2. It is a carbon oxohalide. This gas, like its analog phosgene, is colourless and highly toxic. The molecule is planar with C2v symmetry, bond lengths of 1.174 Å (C=O) and 1.312 Å (C–F), and an F–C–F bond angle of 108.0°.

<span class="mw-page-title-main">Dicobalt octacarbonyl</span> Chemical compound

Dicobalt octacarbonyl is an organocobalt compound with composition Co2(CO)8. This metal carbonyl is used as a reagent and catalyst in organometallic chemistry and organic synthesis, and is central to much known organocobalt chemistry. It is the parent member of a family of hydroformylation catalysts. Each molecule consists of two cobalt atoms bound to eight carbon monoxide ligands, although multiple structural isomers are known. Some of the carbonyl ligands are labile.

In organic chemistry, the Kumada coupling is a type of cross coupling reaction, useful for generating carbon–carbon bonds by the reaction of a Grignard reagent and an organic halide. The procedure uses transition metal catalysts, typically nickel or palladium, to couple a combination of two alkyl, aryl or vinyl groups. The groups of Robert Corriu and Makoto Kumada reported the reaction independently in 1972.

<span class="mw-page-title-main">Organonickel chemistry</span> Branch of organometallic chemistry

Organonickel chemistry is a branch of organometallic chemistry that deals with organic compounds featuring nickel-carbon bonds. They are used as a catalyst, as a building block in organic chemistry and in chemical vapor deposition. Organonickel compounds are also short-lived intermediates in organic reactions. The first organonickel compound was nickel tetracarbonyl Ni(CO)4, reported in 1890 and quickly applied in the Mond process for nickel purification. Organonickel complexes are prominent in numerous industrial processes including carbonylations, hydrocyanation, and the Shell higher olefin process.

In chemistry, carbonylation refers to reactions that introduce carbon monoxide (CO) into organic and inorganic substrates. Carbon monoxide is abundantly available and conveniently reactive, so it is widely used as a reactant in industrial chemistry. The term carbonylation also refers to oxidation of protein side chains.

Organoplatinum chemistry is the chemistry of organometallic compounds containing a carbon to platinum chemical bond, and the study of platinum as a catalyst in organic reactions. Organoplatinum compounds exist in oxidation state 0 to IV, with oxidation state II most abundant. The general order in bond strength is Pt-C (sp) > Pt-O > Pt-N > Pt-C (sp3). Organoplatinum and organopalladium chemistry are similar, but organoplatinum compounds are more stable and therefore less useful as catalysts.

<span class="mw-page-title-main">Cobalt tetracarbonyl hydride</span> Chemical compound

Cobalt tetracarbonyl hydride is an organometallic compound with the formula HCo(CO)4. It is a volatile, yellow liquid that forms a colorless vapor and has an intolerable odor. The compound readily decomposes upon melt and in absentia of high CO partial pressures forms Co2(CO)8. Despite operational challenges associated with its handling, the compound has received considerable attention for its ability to function as a catalyst in hydroformylation. In this respect, HCo(CO)4 and related derivatives have received significant academic interest for their ability to mediate a variety of carbonylation (introduction of CO into inorganic compounds) reactions.

<span class="mw-page-title-main">Rhodocene</span> Organometallic chemical compound

Rhodocene is a chemical compound with the formula [Rh(C5H5)2]. Each molecule contains an atom of rhodium bound between two planar aromatic systems of five carbon atoms known as cyclopentadienyl rings in a sandwich arrangement. It is an organometallic compound as it has (haptic) covalent rhodium–carbon bonds. The [Rh(C5H5)2] radical is found above 150 °C (302 °F) or when trapped by cooling to liquid nitrogen temperatures (−196 °C [−321 °F]). At room temperature, pairs of these radicals join via their cyclopentadienyl rings to form a dimer, a yellow solid.

<span class="mw-page-title-main">Metal-phosphine complex</span>

A metal-phosphine complex is a coordination complex containing one or more phosphine ligands. Almost always, the phosphine is an organophosphine of the type R3P (R = alkyl, aryl). Metal phosphine complexes are useful in homogeneous catalysis. Prominent examples of metal phosphine complexes include Wilkinson's catalyst (Rh(PPh3)3Cl), Grubbs' catalyst, and tetrakis(triphenylphosphine)palladium(0).

Nickel compounds are chemical compounds containing the element nickel which is a member of the group 10 of the periodic table. Most compounds in the group have an oxidation state of +2. Nickel is classified as a transition metal with nickel(II) having much chemical behaviour in common with iron(II) and cobalt(II). Many salts of nickel(II) are isomorphous with salts of magnesium due to the ionic radii of the cations being almost the same. Nickel forms many coordination complexes. Nickel tetracarbonyl was the first pure metal carbonyl produced, and is unusual in its volatility. Metalloproteins containing nickel are found in biological systems.

References

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  2. Nickel tetracarbonyl, carcinogenicity
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  4. The Merck Index (7th ed.). Merck.
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  14. Board on Environmental Studies and Toxicology (2008). "Nickel Carbonyl: Acute Exposure Guideline Levels". Acute Exposure Guideline Levels for Selected Airborne Chemicals. Vol. 6. National Academies Press. pp. 213–259. doi:10.17226/12018. ISBN   978-0-309-11213-0. PMID   25032325.
  15. Stedman, D. H.; Hikade, D. A.; Pearson, R. Jr.; Yalvac, E. D. (1980). "Nickel Carbonyl: Decomposition in Air and Related Kinetic Studies". Science . 208 (4447): 1029–1031. Bibcode:1980Sci...208.1029S. doi:10.1126/science.208.4447.1029. PMID   17779026. S2CID   31344783.
  16. "40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities" (PDF) (July 1, 2008 ed.). Government Printing Office. Archived from the original (PDF) on February 25, 2012. Retrieved October 29, 2011.{{cite journal}}: Cite journal requires |journal= (help)

Further reading