Nickel tetracarbonyl

Source: Wikipedia, the free encyclopedia.
Nickel tetracarbonyl
Nickel carbonyl
Nickel carbonyl
Nickel carbonyl
Nickel carbonyl
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 Edit this at Wikidata
EC Number
  • 236-669-2
3135
RTECS number
  • QR6300000
UNII
UN number 1259
  • InChI=1S/4CO.Ni/c4*1-2; checkY
    Key: AWDHUGLHGCVIEG-UHFFFAOYSA-N checkY
  • 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
Appearance colorless 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
320 J K−1 mol−1
Std enthalpy of
formation
(ΔfH⦵298)
 −632 kJ/mol
Std enthalpy of
combustion
(ΔcH⦵298)
 −1180 kJ/mol
Hazards
Occupational safety and health (OHS/OSH):
Main hazards
 Potential occupational carcinogen[2]
GHS labelling:
Acutely toxic Health hazard Flammable Dangerous for the environment
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 four-colored diamondHealth 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).
checkY verify (what is checkY☒N ?)

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]

Structure and bonding

In nickel tetracarbonyl, the

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

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

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.

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.

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

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

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]

In popular culture

"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

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.

References

  1. ^ a b c d e f NIOSH Pocket Guide to Chemical Hazards. "#0444". National Institute for Occupational Safety and Health (NIOSH).
  2. ^ Nickel tetracarbonyl, carcinogenicity
  3. ^ a b "Nickel carbonyl". Immediately Dangerous to Life or Health Concentrations (IDLH). National Institute for Occupational Safety and Health (NIOSH).
  4. The Merck Index (7th ed.). Merck
    .
  5. doi:10.1063/1.437911
    .
  6. doi:10.1039/CT8905700749
    .
  7. doi:10.1038/059063a0
    .
  8. ^
    ISBN 978-3527306732
    .
  9. ISBN 0-08-025269-9
    .
  10. ^ F. Seel (1963). "Nickel Carbonyl". In G. Brauer (ed.). Handbook of Preparative Inorganic Chemistry. Vol. 2 (2nd ed.). NY: Academic Press. pp. 1747–1748.
  11. ISBN 3-527-28165-7
    .
  12. ISBN 0471936235
    .
  13. ^ Semmelhack, M. F.; Helquist, P. M. (1972). "Reaction of Aryl Halides with π-Allylnickel Halides: Methallylbenzene". Organic Syntheses. 52: 115; Collected Volumes, vol. 6, p. 722.
  14. PMID 25032325
    .
  15. 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

External links
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