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| Names | |||
|---|---|---|---|
| IUPAC name Tetracarbonylnickel | |||
| Other names Nickel tetracarbonyl Nickel carbonyl (1:4) | |||
| Identifiers | |||
3D model (JSmol) | |||
| 6122797 | |||
| ChEBI | |||
| ChemSpider |
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| ECHA InfoCard | 100.033.322 | ||
| EC Number |
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| 3135 | |||
| RTECS number |
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| UNII | |||
| UN number | 1259 | ||
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| 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 mostorganic solvents soluble innitric 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(S⦵298) | 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: | |||
    | |||
| 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) | |||
| Flash point | 4 °C (39 °F; 277 K) | ||
| 60 °C (140 °F; 333 K) | |||
| Explosive limits | 2–34% | ||
| Lethal dose or concentration (LD, LC): | |||
LC50 (median concentration) | 266 ppm (cat, 30 min) 35 ppm (rabbit, 30 min) 94 ppm (mouse, 30 min) 10 ppm (mouse, 10 min)[3] | ||
LCLo (lowest published) | 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 | |||
Relatedmetal carbonyls |
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Except where otherwise noted, data are given for materials in theirstandard state (at 25 °C [77 °F], 100 kPa). | |||
Nickel carbonyl (IUPAC name:tetracarbonylnickel) is anickel(0) organometallic compound with theformula Ni(CO)4. This colorless liquid is the principalcarbonyl ofnickel. It is anintermediate in theMond process for producing very high-puritynickel and areagent inorganometallic 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 hightoxicity, compounded with high volatility and rapid skin absorption.[4]
In nickel tetracarbonyl, theoxidation 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 the18-electron rule. The molecule istetrahedral, with fourcarbonyl (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]
Ni(CO)4 was first synthesised in 1890 byLudwig 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 ofvanadium,chromium,manganese,iron, andcobalt. 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]
Ni(CO)4 is not readily available commercially. It is conveniently generated in the laboratory bycarbonylation of commercially availablebis(cyclooctadiene)nickel(0).[9] It can also be prepared by reduction of ammoniacal solutions of nickel sulfate withsodium dithionite under an atmosphere of CO.[10]
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 theMond process for the purification of nickel or plating onto surfaces. Thermal decomposition commences near 180 °C (356 °F) and increases at higher temperature.[8]
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 astriphenylphosphine react to giveNi(CO)3(PPh3) andNi(CO)2(PPh3)2.Bipyridine and related ligands behave similarly.[11] The monosubstitution of nickel tetracarbonyl with other ligands can be used to determine theTolman electronic parameter, a measure of the electron donating or withdrawing ability of a given ligand.
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Treatment withhydroxides 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]
Nickel carbonyl can beoxidized. Chlorine oxidizes nickel carbonyl intoNiCl2, 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 unsaturatedesters upon treatment with Ni(CO)4 followed by sodium methoxide. Such reactions also probably proceed viaoxidative 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
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. ItsLC50 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 canautoignite. The vapordecomposes 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 ofheadaches andchest pain lasting a few hours, usually followed by a short remission. The second phase is achemical 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 oracute kidney injury.Convalescence is often extremely protracted, often complicated by exhaustion,depression anddyspnea on exertion. Permanent respiratory damage is unusual. Thecarcinogenicity of Ni(CO)4 is a matter of debate, but is presumed to be significant.
It is classified as anextremely 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 ofQuincy, 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 novellaAmanda Morgan byGordon 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 themangaDr. Stone, a machine is made that purifies nickel via theMond Process. It is mentioned that the process creates a "fatal toxin" (nickel carbonyl).
In the 2019 novelDelta-v fromNew York Times bestselling authorDaniel 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 tonear Earth orbit, and used for in-situ fabrication of a spacecraft, via decomposition in vacuum.
| Authority control databases: National |
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