Nickel carbonyl
General
Systematic name	Tetracarbonylnickel(0)
Other names	Nickel tetracarbonyl
Molecular formula	Ni(CO)4
Molar mass	170.7 g/mol
Appearance	colorless liquid
CAS number	[13463-39-3]
EINECS number	236-669-2
Properties
Density and phase	1.3 g/ml, liquid
Solubility in water	Immiscible
Melting point	-19 °C
Boiling point	43 °C
Viscosity	? cP at ? °C
Structure
Molecular shape	Tetrahedral
Coordination geometry	Tetrahedral
Dipole moment	zero
Thermodynamic data
Standard enthalpy of formation ΔfH°liquid	-632 kJ/mol
Standard enthalpy of combustion ΔcH°liquid	-1180 kJ/mol
Standard molar entropy S°liquid	320 J.K−1.mol−1
Safety data
EU classification	Flammable (F) Very toxic (T+) Carc. Cat. 3 Repr. Cat. 2 Dangerous for the environment (N)
R-phrases	R61, R11, R26 R40, R50/53
S-phrases	S53, S45, S60, S61
NFPA 704
PEL-TWA (OSHA)	0.001 ppm (0.007 mg/m3)
IDLH (NIOSH)	approx. 2 ppm (14 mg/m3)
Flash point	-20 °C
Autoignition temperature	60 °C
Explosive limits	2–34%
RTECS number	QR6300000
Supplementary data page
Structure and properties	n, εr, etc.
Thermodynamic data	Phase behaviour Solid, liquid, gas
Spectral data	UV, IR, NMR, MS
Related compounds
Related metal carbonyls	Chromium hexacarbonyl Dimanganese decacarbonyl Iron pentacarbonyl Dicobalt octacarbonyl
Related compounds	?
Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) Infobox disclaimer and references

Nickel carbonyl, or tetracarbonylnickel is the compound Ni(CO)₄. Somewhat unusually for a metal compound, Ni(CO)₄ is a colorless, volatile liquid at room temperature. It is highly toxic, earning it the nickname "liquid death". Ni(CO)₄ is of historic significance as well as practical and theoretical interest. Image File history File links Nickel_carbonyl. ... IUPAC nomenclature is a system of naming chemical compounds and of describing the science of chemistry in general. ... A chemical formula (also called molecular formula) is a concise way of expressing information about the atoms that constitute a particular chemical compound. ... Molar mass is the mass of one mole of a chemical element or chemical compound. ... CAS registry numbers are unique numerical identifiers for chemical compounds, polymers, biological sequences, mixtures and alloys. ... The EINECS number (for European Inventory of Existing Chemical Substances) is a registry number given to each chemical substance commercially available in the European Union between 1 January 1971 and 18 September 1981. ... Density (symbol: ρ - Greek: rho) is a measure of mass per unit of volume. ... In the physical sciences, a phase is a set of states of a macroscopic physical system that have relatively uniform chemical composition and physical properties (i. ... It has been suggested that this article or section be merged with Solution. ... Water has the chemical formula H2O, meaning that one molecule of water is composed of two hydrogen atoms and one oxygen atom. ... The melting point of a solid is the temperature at which it changes state from solid to liquid. ... The boiling point of a substance is the temperature at which it can change its state from a liquid to a gas throughout the bulk of the liquid. ... The pitch drop experiment at the University of Queensland. ... The poise (P) is the cgs unit of viscosity, 1 P = 1 g·cm-1·s-1 The SI analog is 1 pascal second (Pa·s) = 1 kg·m-1·s-1 = 10 P. It is named after Jean Louis Marie Poiseuille. ... four sp³ orbitals three sp² orbitals In chemistry, hybridisation is the mixing of atomic orbitals belonging to a same electron shell to form new orbitals suitable for the qualitative description of atomic bonding properties. ... The coordination geometry of an atom is the geometrical pattern formed by its neighbors in a molecule or a crystal. ... The Earths magnetic field, which is approximately a dipole. ... The standard enthalpy of formation or standard heat of formation of a compound is the change of enthalpy that accompanies the formation of 1 mole of a substance in its standard state from its constituent elements in their standard states (the most stable form of the element at 1 atmosphere... Standard enthalpy of Combustion is the Enthalpy change when one mole of a substance is totally combusted in oxygen, and is measured at 298K and 1 atmospheric pressure. ... In chemistry, the standard molar entropy is the entropy content of one mole of substance, under conditions of standard temperature and pressure. ... Council Directive 67/548/EEC of 27 June 1967 on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substances (as amended) is the main source of European Union law concerning chemical safety. ... R-phrases are defined in Annex III of European Union Directive 67/548/EEC: Nature of special risks attributed to dangerous substances and preparations. ... S-phrases are defined in Annex IV of European Union Directive 67/548/EEC: Safety advice concerning dangerous substances and preparations. ... NFPA 704 is a standard maintained by the U.S. National Fire Protection Association. ... Image File history File links File history Legend: (cur) = this is the current file, (del) = delete this old version, (rev) = revert to this old version. ... Image File history File links File history Legend: (cur) = this is the current file, (del) = delete this old version, (rev) = revert to this old version. ... Image File history File links File history Legend: (cur) = this is the current file, (del) = delete this old version, (rev) = revert to this old version. ... The Permissible Exposure Limit (PEL or OSHA PEL) is a legal limit in the United States for personal exposure to a substance, usually expressed in parts per million (ppm). ... The United States Occupational Safety and Health Administration (OSHA) was created by Congress under the Occupational Safety and Health Act, signed by President Richard M. Nixon on December 29, 1970. ... Immediately Dangerous to Life and Health (IDLH or NIOSH IDLH) is a limit for personal exposure to a substance defined by the United States National Institute for Occupational Safety and Health (NIOSH), normally expressed in parts per million (ppm). ... The National Institute for Occupational Safety and Health (NIOSH) is the United States federal agency responsible for conducting research and making recommendations for the prevention of work-related injury and illness. ... The flash point of a fuel is the lowest temperature at which it can form an ignitable mix with air. ... The autoignition temperature of a substance is the lowest temperature at which it will spontaneously combust in a normal atmosphere, without an external source of ignition, such as a flame or spark. ... The explosive limit of a gas or a vapour, is the limiting concentration (in air) that is needed for the gas to ignite and explode. ... RTECS, also known as Registry of Toxic Effects of Chemical Substances, is a database of toxicity information compiled from the open scientific literature that is available for charge. ... The refractive index of a material is the factor by which the phase velocity of electromagnetic radiation is slowed relative to vacuum. ... The dielectric constant εr (represented as or K in some cases) is defined as the ratio: where εs is the static permittivity of the material in question, and ε0 is the vacuum permittivity. ... Ultraviolet-Visible Spectroscopy or Ultraviolet-Visible Spectrophotometry (UV/ VIS) involves the spectroscopy of photons (spectrophotometry). ... IR spectrum of a thin film of liquid ethanol. ... Nuclear Magnetic Resonance Spectroscopy is the name given to the technique which exploits the magnetic properties of nuclei. ... Mass spectrometry is an analytical technique to measure the mass-to-charge ratio (m/q) of ions. ... Metal carbonyls are organometallic complexes of transition metals with carbon monoxide. ... Iron pentacarbonyl is a toxic and highly flammable iron compound with chemical formula Fe(CO)5 and CAS number 13463-40-6. ... In chemistry, the standard state of a material is its state at 1 bar (100 kilopascals) and 25 degrees Celsius (298. ...

Structure and bonding

Like many other binary metal carbonyls has 18 valence electrons. Other famous examples include iron pentacarbonyl and molybdenum carbonyl. These compounds feature covalent bonds between the metal and the carbon end of CO. Metal carbonyls adopt highly symmetrical structures, resulting in their high volatility. Iron pentacarbonyl is a toxic and highly flammable iron compound with chemical formula Fe(CO)5 and CAS number 13463-40-6. ... Molybdenum hexacarbonyl (also called molybdenum carbonyl or molybdenumhexacarbonyl) is an organometallic compound. ... Covalently bonded hydrogen and carbon in a molecule of methane. ... CO can stand for: Carbon monoxide (molecular formula) Central Office (telecommunications and telephony) Chesapeake and Ohio Railroad (AAR reporting mark CO) Colombia (ISO 3166-1 digram and NATO country code) Colorado ( U.S. state postal symbol) Commanding Officer (military) Conscientious Objector (military) Continental Airlines (IATA airline code) Collaborative Browsing Co...

Preparation

Nickel metal reacts at room temperature with carbon monoxide (CO) to form the tetracarbonyl. On moderate heating, such as contact with a hot glass surface, Ni(CO)₄ decomposes back to carbon monoxide and nickel metal. These two reactions form the basis for the Mond process for preparing pure nickel. Carbon monoxide, chemical formula CO, is a colorless, odorless, tasteless, flammable and highly toxic gas. ... Dr Ludwig Mond (born March 7, 1839, Kassel; died December 11, 1909, London) was an important German-born British chemist and industrialist. ...

Chemical reactions

Like other low-valent metal carbonyls, Ni(CO)₄ undergoes CO substitution reactions and can be oxidized. Donor ligands such as PPh₃ react to give Ni(CO)₃(PPh₃) and Ni(CO)₂(PPh₃)₂. Bipyridine and related ligands behave similarly. These reactions proceed via an initial loss of CO to give a reactive 16e Ni(CO)₃ intermediate that scavanges the donor ligand. In chemistry, a ligand is an atom, ion or functional group that is bonded to one or more central atoms or ions, usually metals generally through co-ordinate covalent bond. ... Flash point 180 °C RTECS number SZ3500000 Supplementary data page Structure and properties n, εr, etc. ...

Chlorine oxidizes Ni(CO)₄ to give NiCl₂ and release CO. Other halogens behave analogously. This reaction provides a convenient method for destroying Ni(CO)₄.

Reduction or treatment with hydroxide affords clusters such as [Ni₅(CO)₁₂]^2- and [Ni₆(CO)₁₂]^2-.

Most interesting in the area of organic synthesis are reactions of Ni(CO)₄ with alkyl and aryl halides, which often result in cabonylated organic products. Vinyl halides, e.g. PhCH=CHBr, are converted to the unsaturated esters using Ni(CO)₄ followed by NaOMe. Such reactions also probably proceed via Ni(CO)₃, which undergoes oxidative addition. For the Biblical Ester, see Esther. ... Oxidative addition and reductive elimination are two important classes of reactions in organometallic chemistry. ...

Metal carbonyls are also susceptible to attack by nucleophiles at carbon. Thus, treatment of Ni(CO)₄ with some nucleophiles (Nu^-) results in acyl derivatives, e.g. [Ni(CO)₃C(O)Nu)]^-.

Toxicology and safety considerations

Ni(CO)₄ is considered highly hazardous, much more so than its CO content, apparently reflecting the effects of the nickel that is released in the body. Ni(CO)₄ may be fatal if absorbed through the skin or more likely, ingested due to its high volatility. The vapours of Ni(CO)₄ can autoignite.

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. Acute renal failure (ARF) is a rapid loss of renal function due to damage to the kidneys, resulting in retention of nitrogenous (urea and creatinine) and non-nitrogenous waste products that are normally excreted by the kidney. ... Clinical depression is a state of sadness or melancholia that has advanced to the point of being disruptive to an individuals social functioning and/or activities of daily living. ... Dyspnea (Latin dyspnoea, Greek dyspnoia from dyspnoos - short of breath) or shortness of breath (SOB) is perceived difficulty breathing or pain on breathing. ...

External links

• International Chemical Safety Card 0064
• National Pollutant Inventory - Nickel carbonyl fact sheet
• NIOSH Pocket Guide to Chemical Hazards
• European Chemicals Bureau
• IARC Monograph "Nickel and Nickel compounds"
• NIST Standard Reference Database

References

• Lascelles,Keith; Morgan, Lindsay G.; & Nicholls, David (1991). "Nickel Compounds". Ullmann's Encyclopedia of Industrial Chemistry A17 (5): 235-249.
• EROS Encyclopedia of Reagents for Organic Synthesis, John Wiley & Sons, 2003.