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Nickel tetracarbonyl

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Title: Nickel tetracarbonyl  
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Subject: Metal carbonyl, Carbonyl metallurgy, Nickel(II) nitrite, Nickel(II) titanate, Nickel compounds
Collection: Carbonyl Complexes, Iarc Group 1 Carcinogens, Nickel Compounds, Organonickel Compounds
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Nickel tetracarbonyl

Nickel tetracarbonyl
Nickel carbonyl
Nickel carbonyl
Nickel carbonyl
Names
IUPAC name
Tetracarbonylnickel
Other names
Nickel tetracarbonyl
Nickel carbonyl
Identifiers
 Y
ChEBI  Y
ChemSpider  Y
EC number 236-669-2
Jmol-3D images Image
PubChem
RTECS number QR6300000
UN number 1259
Properties
Ni(CO)4
Molar mass 170.73 g/mol
Appearance colorless or very-pale-yellow liquid[1]
diamagnetic
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)
.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
−632 kJ/mol
−1180 kJ/mol
Hazards
Safety data sheet ICSC 0064
Flammable ('F)
Carc. Cat. 3
Repr. Cat. 2
Very Toxic (T+)
Dangerous for the environment (N)
R-phrases R50/53
S-phrases S53, S45, S60, S61
NFPA 704
3
4
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)[2]
360 ppm (dog, 90 min)
30 ppm (human, 30 min)
42 ppm (rabbit, 30 min)
7 ppm (mouse, 30 min)[2]
US health exposure limits (NIOSH):
PEL (Permissible)
TWA 0.001 ppm (0.007 mg/m3)[1]
REL (Recommended)
TWA 0.001 ppm (0.007 mg/m3)[1]
Ca [2 ppm][1]
Related compounds
Related metal carbonyls
Iron pentacarbonyl
Dicobalt octacarbonyl
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
 Y  (: Y/N?)

Nickel carbonyl (

  • International Chemical Safety Card 0064
  • National Pollutant Inventory - Nickel carbonyl fact sheet
  • NIOSH Pocket Guide to Chemical Hazards
  • IARC Monograph "Nickel and Nickel compounds"

External links

  • Shi, Z. (1991). "Nickel Carbonyl: Toxicity and Human Health". Science of the Total Environment 148 (2–3): 293–298.  
  • Sunderman, F. W. (1989). "A Pilgrimage into the Archives of Nickel Toxicology". Annals of Clinical and Laboratory Science 19 (1): 1–16.  
  • Armit, H. W. (1907). "The Toxicology of Nickel Carbonyl. Part I" (pdf). Journal of Hygiene 7 (4): 525–551.  
  • Armit, H. W. (1908). "The Toxicology of Nickel Carbonyl. Part II" (pdf). Journal of Hygiene 8 (5): 565–610.  
  • Barceloux, D. G.; Barceloux, Donald (1999). "Nickel". Clinical Toxicology 37 (2): 239–258.  

Further reading

  1. ^ a b c d e f "NIOSH Pocket Guide to Chemical Hazards #0444".  
  2. ^ a b "Nickel carbonyl". Immediately Dangerous to Life and Health.  
  3. ^  
  4. ^ Hedberg, L.; Iijima, T.; Hedberg, K. (1979). "Nickel tetracarbonyl, Ni(CO)4. I. Molecular Structure by Gaseous Electron Diffraction. II. Refinement of Quadratic Force Field". The Journal of Chemical Physics 70 (7): 3224–3229.  
  5. ^  
  6. ^ "The Extraction of Nickel from its Ores by the Mond Process".  
  7. ^ a b Lascelles, K.; Morgan, L. G.; Nicholls, D.; Beyersmann, D. (2005), "Nickel Compounds",  
  8. ^ P. W. Jolly "Nickel Tetracarbonyl" in Comprehensive Organometallic Chemistry I" Edward W. Abel, F. Gordon A. Stone, Geoffrey Wilkinson, eds., 1982, Pergamon Press, Oxford. ISBN 0.08-025269-9.
  9. ^ Elschenbroich, C.; Salzer, A. (1992). Organometallics: A Concise Introduction (2nd ed.). Weinheim:  
  10. ^ Pinhas, A. R. (2003). "Tetracarbonylnickel". Encyclopedia of Reagents for Organic Synthesis. Encyclopedia of Reagents for Organic Synthesis. John Wiley & Sons.  
  11. ^ Semmelhack, M. F.; Helquist, P. M. (1972). "Reaction of Aryl Halides with π-Allylnickel Halides: Methallylbenzene".  
  12. ^ Board on Environmental Studies and Toxicology (2008). "Nickel Carbonyl: Acute Exposure Guideline Levels". Acute Exposure Guideline Levels for Selected Airborne Chemicals 6.  
  13. ^ Stedman, D. H.; Hikade, D. A.; Pearson, R. Jr.; Yalvac, E. D. (1980). "Nickel Carbonyl: Decomposition in Air and Related Kinetic Studies".  

References

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 renal failure. 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.

The vapours of Ni(CO)4 can autoignite. The vapor decomposes quickly in air, lasting only about a minute.[13]

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.[12]

Toxicology and safety considerations

2 Ni(CO)4 + 2 ClCH2CH=CH2 → Ni2(μ-Cl)23-C3H5)2 + 8 CO

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 pi-allyl nickel compounds, such as (allyl)2Ni2Cl2:[11]

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 destroying unwanted portions of the toxic compound.

Reactions with electrophiles and oxidizing agents

Thus, treatment of Ni(CO)4 with carbon nucleophiles (Nu) results in acyl derivatives such as [Ni(CO)3C(O)Nu)].[10]

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.

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.[9] 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.

Reactions with nucleophiles and reducing agents

On moderate heating, Ni(CO)4 decomposes to carbon monoxide and nickel metal. Combined with the easy formation from CO and even impure nickel, this decomposition is the basis for the Mond process for the purification of nickel. Thermal decomposition commences near 180 °C and increases at higher temperature.[7]

Thermal decarbonylation

Spheres of nickel made by the Mond process

Reactions

Ni(CO)4 is not readily available commercially. It is conveniently generated in the laboratory by carbonylation of commercially available bis(cyclooctadiene)nickel(0).[8]

At 323 K (50 °C (122 °F)), carbon monoxide is passed over impure nickel. The optimal rate occurs at 130 °C.[7]

Ni(CO)4 was first synthesised in 1890 by Ludwig Mond by the direct reaction of nickel metal with CO.[5] This pioneering work foreshadowed the existence of many other metal carbonyl compounds, including those of V, Cr, Mn, Fe, and Co. It was also applied industrially to the purification of nickel by the end of the 19th century.[6]

Preparation

In nickel tetracarbonyl, the oxidation state for nickel is assigned as zero. The formula conforms to 18-electron rule. The molecule is tetrahedral, with four carbonyl (carbon monoxide) ligands attached to nickel. The CO ligands, in which the C and the O are connected by triple bonds, are covalently bonded to the nickel atom via the carbon ends. 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.[4]

Structure and bonding

Contents

  • Structure and bonding 1
  • Preparation 2
  • Reactions 3
    • Thermal decarbonylation 3.1
    • Reactions with nucleophiles and reducing agents 3.2
    • Reactions with electrophiles and oxidizing agents 3.3
  • Toxicology and safety considerations 4
  • References 5
  • Further reading 6
  • External links 7

[3]

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