| Revision as of 12:40, 15 February 2012 editBeetstra (talk | contribs)Edit filter managers, Administrators172,031 edits Saving copy of the {{chembox}} taken from revid 474325802 of page Nickel_tetracarbonyl for the Chem/Drugbox validation project (updated: ''). |
Latest revision as of 10:55, 15 October 2024 edit 31.220.212.249 (talk)No edit summary |
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{{Short description|Chemical compound}} |
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{{ambox | text = This page contains a copy of the infobox ({{tl|chembox}}) taken from revid of page ] with values updated to verified values.}} |
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{{chembox |
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{{chembox |
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| verifiedrevid = 449013121 |
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| verifiedrevid = 476995560 |
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| Name = Nickel tetracarbonyl |
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| Name = Nickel tetracarbonyl |
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| ImageFile = Nickel-carbonyl-2D.png |
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| ImageFile1 = Nickel-tetracarbonyl-2D.png |
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| ImageSize = 150px |
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| ImageSize1 = 150px |
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| ImageName = Nickel carbonyl |
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| ImageName1 = Nickel carbonyl |
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| ImageFile1 = Nickel-carbonyl-3D-vdW.png |
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| ImageFileL2 = Nickel-tetracarbonyl-3D-balls.png |
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| ImageSize1 = 150px |
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| ImageSizeL2 = 75px |
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| ImageName1 = Nickel carbonyl |
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| ImageNameL2 = Nickel carbonyl |
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| ImageFileR2 = Nickel-carbonyl-3D-vdW.png |
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| IUPACName = Tetracarbonylnickel |
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| ImageSizeR2 = 75px |
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| OtherNames = Nickel carbonyl |
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| ImageNameR2 = Nickel carbonyl |
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| Section1 = {{Chembox Identifiers |
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| IUPACName = Tetracarbonylnickel |
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| ChemSpiderID_Ref = {{chemspidercite|correct|chemspider}} |
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| OtherNames = Nickel tetracarbonyl<br />Nickel carbonyl (1:4) |
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| ChemSpiderID = 21865021 |
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Liquid Death |
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|Section1={{Chembox Identifiers |
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| ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} |
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| ChemSpiderID = 24253 |
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| InChI = 1/4CO.Ni/c4*1-2;/rC4NiO4/c6-1-5(2-7,3-8)4-9 |
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| InChI = 1/4CO.Ni/c4*1-2;/rC4NiO4/c6-1-5(2-7,3-8)4-9 |
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| InChIKey = AWDHUGLHGCVIEG-ARWXMKMZAJ |
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| InChIKey = AWDHUGLHGCVIEG-ARWXMKMZAJ |
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| SMILES = C(#O)(C#O)(C#O)C#O |
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| SMILES = #C(C#)(C#)C# |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI_Ref = {{stdinchicite|correct|chemspider}} |
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| StdInChI = 1S/4CO.Ni/c4*1-2; |
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| StdInChI = 1S/4CO.Ni/c4*1-2; |
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| StdInChIKey = AWDHUGLHGCVIEG-UHFFFAOYSA-N |
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| StdInChIKey = AWDHUGLHGCVIEG-UHFFFAOYSA-N |
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| CASNo = 13463-39-3 |
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| CASNo = 13463-39-3 |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| CASNo_Ref = {{cascite|correct|CAS}} |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI_Ref = {{ebicite|correct|EBI}} |
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| ChEBI = 30372 |
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| ChEBI = 30372 |
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| PubChem = 26039 |
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| PubChem = 26039 |
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| EINECS = 236-669-2 |
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| EINECS = 236-669-2 |
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| RTECS = QR6300000 |
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| RTECS = QR6300000 |
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| UNNumber = 1259 |
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| UNNumber = 1259 |
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| Gmelin = 3135 |
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| Beilstein = 6122797 |
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| UNII = 1ZYL78UWZN |
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}} |
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| Section2 = {{Chembox Properties |
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|Section2={{Chembox Properties |
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| Formula = Ni(CO)<sub>4</sub> |
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| Formula = Ni(CO)<sub>4</sub> |
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| MolarMass = 170.73 g/mol |
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| MolarMass = 170.73 g/mol |
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| Appearance = colorless or very-pale-yellow liquid <br> ] |
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| Appearance = colorless liquid<ref name=PGCH/> |
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| Odor = musty,<ref name=PGCH/> like brick dust |
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| Density = 1.319 g/cm<sup>3</sup> |
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| Solubility = .018 g/100 mL (10 °C) |
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| Density = 1.319 g/cm<sup>3</sup> |
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| Solubility = 0.018 g/100 mL (10 °C) |
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| SolubleOther = miscible in most ] <br> soluble in ], ] |
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| SolubleOther = miscible in most ] <br /> soluble in ], ] |
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| MeltingPtC = -17.2 |
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| BoilingPtC = 43 |
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| MeltingPtC = −17.2 |
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| Viscosity = 3.05 x 10<sup>-4</sup> Pa s |
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| BoilingPtC = 43 |
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| Viscosity = 3.05 x 10<sup>−4</sup> Pa s |
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| VaporPressure = 315 mmHg (20 °C)<ref name=PGCH/> |
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}} |
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| Section3 = {{Chembox Structure |
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|Section3={{Chembox Structure |
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| MolShape = Tetrahedral |
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| MolShape = Tetrahedral |
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| Coordination = Tetrahedral |
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| Coordination = Tetrahedral |
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| Dipole = zero |
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| Dipole = zero |
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}} |
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}} |
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| Section4 = {{Chembox Thermochemistry |
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|Section4={{Chembox Thermochemistry |
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| DeltaHf = −632 kJ/mol |
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| DeltaHf = −632 kJ/mol |
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| DeltaHc = −1180 kJ/mol |
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| DeltaHc = −1180 kJ/mol |
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| Entropy = 320 J K<sup>−1</sup> mol<sup>−1</sup> |
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| Entropy = 320 J K<sup>−1</sup> mol<sup>−1</sup> |
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}} |
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}} |
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| Section7 = {{Chembox Hazards |
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|Section7={{Chembox Hazards |
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| MainHazards = Potential occupational carcinogen<ref>Nickel tetracarbonyl, carcinogenicity</ref> |
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| ExternalMSDS = |
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| ExternalSDS = |
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| EUClass = Flammable (''''F''')<br/>]<br/>Repr. Cat. 2<br/>Very Toxic ('''T+''')<br/>Dangerous for the environment ('''N''') |
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| GHSPictograms = {{GHS06|Acutely toxic}} {{GHS health hazard|Health hazard}} {{GHS flame|Flammable}} {{GHS09|Dangerous for the environment}} |
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| EUIndex = 028-001-00-1 |
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| HPhrases = {{H-phrases|225|300|301|304|310|330|351|360D|410}} |
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| RPhrases = {{R61}}, {{R11}}, {{R26}}, {{R40}}, {{R50/53}} |
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| PPhrases = {{P-phrases|201|202|210|233|240|241|242|243|260|271|273|280|281|284|303+361+353|304+340|308+313|310|320|370+378|391|403+233|403+235|405|501}} |
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| SPhrases = {{S53}}, {{S45}}, {{S60}}, {{S61}} |
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| NFPA-H = 4 |
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| NFPA-H = 4 |
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| NFPA-F = 3 |
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| NFPA-F = 3 |
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| NFPA-R = 3 |
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| NFPA-R = 3 |
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| FlashPt = 4 °C |
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| FlashPtC = 4 |
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| Autoignition = 60 °C |
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| AutoignitionPtC = 60 |
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| ExploLimits = 2–34% |
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| ExploLimits = 2–34% |
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| IDLH = Ca <ref name=PGCH>{{PGCH|0444}}</ref> |
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| PEL = TWA 0.001 ppm (0.007 mg/m<sup>3</sup>)<ref name=PGCH/> |
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| REL = TWA 0.001 ppm (0.007 mg/m<sup>3</sup>)<ref name=PGCH/> |
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| LCLo = 360 ppm (dog, 90 min)<br />30 ppm (human, 30 min)<br />42 ppm (rabbit, 30 min)<br />7 ppm (mouse, 30 min)<ref name=IDLH>{{IDLH|13463393|Nickel carbonyl}}</ref> |
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| LC50 = 266 ppm (cat, 30 min)<br />35 ppm (rabbit, 30 min)<br />94 ppm (mouse, 30 min)<br />10 ppm (mouse, 10 min)<ref name=IDLH/> |
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| Section8 = {{Chembox Other |
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|Section8={{Chembox Related |
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| OtherFunction = {{ubl|]|]|]|]|]|]|]|]|]|]|]|]|]|]}} |
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| OtherFunctn = ]<br/>] |
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| Function = ]s |
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| OtherFunction_label = ]s |
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| OtherCpds = |
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| OtherCompounds = |
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'''Nickel carbonyl''' (] name: '''tetracarbonylnickel''') is a ] with the ] Ni(CO)<sub>4</sub>. This colorless liquid is the principal ] of ]. It is an ] in the ] for producing very high-purity ] and a ] in ], 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 ], compounded with high volatility and rapid skin absorption.<ref>{{ cite book | title = The Merck Index | edition = 7th | publisher = ] | title-link = The Merck Index }}</ref> |
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==Structure and bonding== |
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In nickel tetracarbonyl, the ] 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 ]. The molecule is ], with four ] (]) ]. ] 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.<ref>{{ cite journal | last1 = Hedberg | first1 = L. | last2 = Iijima | first2 = T. | last3 = Hedberg | first3 = K. | title = Nickel tetracarbonyl, Ni(CO)<sub>4</sub>. I. Molecular Structure by Gaseous Electron Diffraction. II. Refinement of Quadratic Force Field | journal = The Journal of Chemical Physics | year = 1979 | volume = 70 | issue = 7 | pages = 3224–3229 | doi = 10.1063/1.437911 | bibcode = 1979JChPh..70.3224H }}</ref> |
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==Preparation== |
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Ni(CO)<sub>4</sub> was first synthesised in 1890 by ] by the direct reaction of nickel metal with carbon monoxide.<ref>{{ cite journal | last1= Mond|first1= L. |last2 = Langer|first2= C.| last3= Quincke|first3= F.| author-link1 = Ludwig Mond | title = Action of Carbon Monoxide on Nickel | journal = ] | year = 1890 | volume = 57 | pages = 749–753 | doi = 10.1039/CT8905700749 |url= https://zenodo.org/record/2160347 }}</ref> This pioneering work foreshadowed the existence of many other metal carbonyl compounds, including those of ], ], ], ], and ]. It was also applied industrially to the purification of nickel by the end of the 19th century.<ref>{{ cite journal | journal = ] | title = The Extraction of Nickel from its Ores by the Mond Process | year = 1898 | volume = 59 | issue = 1516 | pages = 63–64 | doi = 10.1038/059063a0 | bibcode = 1898Natur..59...63. | doi-access = free }}</ref> |
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At {{convert|323|K|C F}}, carbon monoxide is passed over impure nickel. The optimal rate occurs at 130 °C.<ref name=Ullmann>{{ Ullmann | author = Lascelles, K. | author2 = Morgan, L. G. | author3 = Nicholls, D. | author4 = Beyersmann, D. | title = Nickel Compounds | doi = 10.1002/14356007.a17_235.pub2 }}</ref> |
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===Laboratory routes=== |
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Ni(CO)<sub>4</sub> is not readily available commercially. It is conveniently generated in the laboratory by ] of commercially available ].<ref>{{cite encyclopedia|first=P. W. |last=Jolly |title=Nickel Tetracarbonyl |encyclopedia=Comprehensive Organometallic Chemistry |volume=I |editor1-first=Edward W. |editor1-last=Abel |editor2-link=F. Gordon A. Stone|editor2-first=F. Gordon A. |editor2-last=Stone |editor3-link=Geoffrey Wilkinson|editor3-first=Geoffrey|editor3-last=Wilkinson |date=1982 |publisher=Pergamon Press |location=Oxford |isbn= 0-08-025269-9}}</ref> It can also be prepared by reduction of ammoniacal solutions of nickel sulfate with ] under an atmosphere of CO.<ref>{{cite book|author=F. Seel|chapter=Nickel Carbonyl|title=Handbook of Preparative Inorganic Chemistry|edition=2nd |editor=G. Brauer|publisher=Academic Press|year=1963|place=NY|volume=2|pages=1747–1748}}</ref> |
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==Reactions== |
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===Thermal decarbonylation=== |
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On moderate heating, Ni(CO)<sub>4</sub> 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 ] for the purification of nickel or plating onto surfaces. Thermal decomposition commences near {{convert|180|C}} and increases at higher temperature.<ref name=Ullmann/> |
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===Reactions with nucleophiles and reducing agents=== |
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Like other low-valent metal carbonyls, Ni(CO)<sub>4</sub> 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 ] react to give {{chem2|Ni(CO)3(PPh3)}} and {{chem2|Ni(CO)2(PPh3)2}}. ] and related ligands behave similarly.<ref>{{ cite book | last1 = Elschenbroich |first1=C. | last2 = Salzer |first2=A. | title = Organometallics: A Concise Introduction | edition = 2nd | year = 1992 | publisher = ] | location = Weinheim | isbn = 3-527-28165-7 }}</ref> The monosubstitution of nickel tetracarbonyl with other ligands can be used to determine the ], a measure of the electron donating or withdrawing ability of a given ligand. |
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Treatment with ]s gives clusters such as {{chem2|(2−)}} and {{chem2|(2−)}}. These compounds can also be obtained by reduction of nickel carbonyl. |
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Thus, treatment of Ni(CO)<sub>4</sub> with carbon nucleophiles (Nu<sup>−</sup>) results in acyl derivatives such as {{chem2|−}}.<ref>{{ cite encyclopedia | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | year = 2003 | publisher = John Wiley & Sons | last= Pinhas|first= A. R. | doi = 10.1002/047084289X.rt025m | chapter= Tetracarbonylnickel | isbn = 0471936235 }}</ref> |
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===Reactions with electrophiles and oxidizing agents=== |
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Nickel carbonyl can be ]. Chlorine oxidizes nickel carbonyl into ], releasing CO gas. Other halogens behave analogously. This reaction provides a convenient method for precipitating the nickel portion of the toxic compound. |
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Reactions of Ni(CO)<sub>4</sub> with alkyl and aryl halides often result in carbonylated organic products. ]ic halides, such as PhCH=CHBr, are converted to the unsaturated ] upon treatment with Ni(CO)<sub>4</sub> followed by sodium methoxide. Such reactions also probably proceed via ]. Allylic halides give the π-allylnickel compounds, such as {{chem2|(allyl)2Ni2Cl2}}:<ref>{{ OrgSynth | author = Semmelhack, M. F. | author2 = Helquist, P. M. | title = Reaction of Aryl Halides with π-Allylnickel Halides: Methallylbenzene | year = 1972 | volume = 52 | pages = 115 | collvol = 6 | collvolpages = 722 | prep = cv6p0722 }}</ref> |
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{{chem2|2 Ni(CO)4 + 2 ClCH2CH\dCH2 -> Ni2 (''μ''\-Cl)2(''\h{3}''C3H5)2 + 8 CO}} |
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==Toxicology and safety considerations== |
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The hazards of Ni(CO)<sub>4</sub> 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 ] for a 30-minute exposure has been estimated at 3 ], 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.<ref>{{ cite book | chapter-url = http://books.nap.edu/openbook.php?record_id=12018&page=159 | title = Acute Exposure Guideline Levels for Selected Airborne Chemicals | volume = 6 | year = 2008 | author = Board on Environmental Studies and Toxicology | publisher = ] | pages = 213–259 | chapter = Nickel Carbonyl: Acute Exposure Guideline Levels | doi = 10.17226/12018 | pmid = 25032325 | isbn = 978-0-309-11213-0 }}</ref> |
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The vapours of Ni(CO)<sub>4</sub> can ]. The vapor ] quickly in air, with a half-life of about 40 seconds.<ref>{{ cite journal | last1= Stedman|first1= D. H. | last2 = Hikade|first2= D. A. | last3 = Pearson |first3=R. Jr. | author4 = Yalvac, E. D. | title = Nickel Carbonyl: Decomposition in Air and Related Kinetic Studies | journal = ] | year = 1980 | volume = 208 | issue = 4447 | pages = 1029–1031 | doi = 10.1126/science.208.4447.1029 | pmid = 17779026 |bibcode= 1980Sci...208.1029S |s2cid= 31344783 }}</ref> |
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Nickel carbonyl poisoning is characterized by a two-stage illness. The first consists of ] and ] lasting a few hours, usually followed by a short remission. The second phase is a ] 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 ]. ] is often extremely protracted, often complicated by exhaustion, ] and ] on exertion. Permanent respiratory damage is unusual. The ] of Ni(CO)<sub>4</sub> is a matter of debate, but is presumed to be significant. |
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It is classified as an ] in the United States as defined in Section 302 of the U.S. ] (42 U.S.C. 11002), and is subject to strict reporting requirements by facilities which produce, store, or use it in significant quantities.<ref name="gov-right-know">{{Cite web| publisher = ] | title = 40 C.F.R.: Appendix A to Part 355—The List of Extremely Hazardous Substances and Their Threshold Planning Quantities | url = http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf | edition = July 1, 2008 | access-date = October 29, 2011 | archive-url = https://web.archive.org/web/20120225051612/http://edocket.access.gpo.gov/cfr_2008/julqtr/pdf/40cfr355AppA.pdf | archive-date = February 25, 2012 | url-status = dead }}</ref> |
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==In popular culture== |
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"Requiem for the Living" (1978), an episode of '']'', features a poisoned, dying crime lord who asks Dr. Quincy to autopsy his still-living body. Quincy identifies the poison—nickel carbonyl. |
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In the 1979 novella '']'' by ], 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. |
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In chapter 199 of the ] '']'', a machine is made that purifies nickel via the ]. It is mentioned that the process creates a "fatal toxin" (nickel carbonyl). |
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In the 2019 novel ''Delta-v'' from ''New York Times'' bestselling author ] a team of eight private miners reach a near-earth asteroid to extract volatiles (water, CO<sub>2</sub>, etc.) and metals (iron, nickel and cobalt); these are stored as solid carbonyl for transfer back to ], and used for in-situ fabrication of a spacecraft, via decomposition in vacuum. |
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==References== |
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{{Reflist}} |
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==Further reading== |
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* {{ cite journal | last= Shi|first= Z. | title = Nickel Carbonyl: Toxicity and Human Health | journal = Science of the Total Environment | year = 1991 | volume = 148 | issue = 2–3 | pages = 293–298 | pmid = 8029705 | doi = 10.1016/0048-9697(94)90406-5 }} |
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* {{ cite journal | last= Sunderman|first= F. W. | title = A Pilgrimage into the Archives of Nickel Toxicology | journal = Annals of Clinical and Laboratory Science | year = 1989 | volume = 19 | issue = 1 | pages = 1–16 | pmid = 2644888 }} |
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* {{ cite journal | last=Armit|first= H. W. | title = The Toxicology of Nickel Carbonyl. Part I | journal = Journal of Hygiene | year = 1907 | volume = 7 | issue = 4 | pages = 525–551 | pmid = 20474327 | pmc = 2236193 | doi = 10.1017/S0022172400033507 }} |
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* {{ cite journal | last= Armit|first= H. W. | title = The Toxicology of Nickel Carbonyl. Part II | journal = Journal of Hygiene | year = 1908 | volume = 8 | issue = 5 | pages = 565–610 | pmid = 20474374 | pmc = 2167169 | doi = 10.1017/S0022172400015989 }} |
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* {{ cite journal | last1= Barceloux|first1= D. G. | last2 = Barceloux | first2 = Donald | title = Nickel | journal = Clinical Toxicology | year = 1999 | volume = 37 | issue = 2 | pages = 239–258 | pmid = 10382559 | doi = 10.1081/CLT-100102423 }} |
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==External links== |
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{{Chemical agents}} |
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{{Nickel compounds}} |
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{{Carbonyl complexes}} |
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{{Authority control}} |
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