| 词条 | Molybdenum hexacarbonyl |
| 释义 |
| Verifiedfields = changed | Watchedfields = changed | verifiedrevid = 268875245 | ImageFileL1 = Molybdenum-hexacarbonyl-2D.png | ImageFileL1_Ref = {{chemboximage|correct|??}} | ImageSizeL1 = 121 | ImageNameL1 = Stereo, skeletal formula of molybdenum hexacarbonyl | ImageFileR1 = Molybdenum-hexacarbonyl-from-xtal-3D-balls.png | ImageFileR1_Ref = {{chemboximage|correct|??}} | ImageSizeR1 = 121 | ImageNameR1 = Ball and stick model of molybdenum hexacarbonyl | ImageFile2 = Mocarbonyl.JPG | ImageFile2_Ref = {{chemboximage|correct|??}} | ImageSize2 = 244 | ImageName2 = Sample of molybdenum hexacarbonyl | IUPACName = Hexacarbonylmolybdenum(0) | SystematicName = Hexacarbonylmolybdenum[1] |Section1={{Chembox Identifiers | CASNo = 13939-06-5 | CASNo_Ref = {{cascite|correct|CAS}} | PubChem = 98885 | ChemSpiderID = 21428397 | ChemSpiderID_Ref = {{chemspidercite|changed|chemspider}} | EINECS = 237-713-3 | UNNumber = 3466 | MeSHName = Hexacarbonylmolybdenum | ChEBI_Ref = {{ebicite|changed|EBI}} | ChEBI = 30508 | Gmelin = 3798, 562210 | SMILES = O=C=[Mo](=C=O)(=C=O)(=C=O)(=C=O)=C=O | StdInChI = 1S/6CO.Mo/c6*1-2; | StdInChI_Ref = {{stdinchicite|changed|chemspider}} | StdInChIKey = KMKBZNSIJQWHJA-UHFFFAOYSA-N | StdInChIKey_Ref = {{stdinchicite|changed|chemspider}} }} |Section2={{Chembox Properties | C=6 | Mo=1 | O=6 | Appearance = Vivid, white, translucent crystals | Density = 1.96 g cm−3 | MeltingPtC = 150 | BoilingPtC = 156 }} |Section3={{Chembox Structure | CrystalStruct = Orthogonal | Coordination = Octahedral | Dipole = 0 D }} |Section4={{Chembox Thermochemistry | DeltaHf = −989.1 kJ mol−1 | DeltaHc = −2123.4 kJ mol−1 }} |Section5={{Chembox Hazards | ExternalSDS = External MSDS | EUClass = {{Hazchem T+}} | RPhrases = {{R26/27/28}} | SPhrases = {{S1/2}}, {{S36/37/39}}, {{S45}} }} |Section6={{Chembox Related | OtherCompounds = Chromium hexacarbonyl Tungsten hexacarbonyl }} }} Molybdenum hexacarbonyl (also called molybdenum carbonyl) is the chemical compound with the formula Mo(CO)6. This colorless solid, like its chromium and tungsten analogues, is noteworthy as a volatile, air-stable derivative of a metal in its zero oxidation state. Structure and propertiesMo(CO)6 adopts an octahedral geometry consisting of six rod-like CO ligands radiating from the central Mo atom. A recurring minor debate in some chemical circles concerns the definition of an "organometallic" compound. Usually, organometallic indicates the presence of a metal directly bonded via a M–C bond to an organic fragment, which must in turn have a C–H bond. By this strict definition, Mo(CO)6 is not organometallic.{{Citation needed|date=May 2016}} PreparationMo(CO)6 is prepared by the reduction of molybdenum chlorides or oxides under a pressure of carbon monoxide,{{Citation needed|date=June 2009}} although it would be unusual to prepare this inexpensive compound in the laboratory. The compound is somewhat air-stable and sparingly soluble in nonpolar organic solvents. OccurrenceMo(CO)6 has been detected in landfills and sewage plants, the reducing, anaerobic environment being conducive to formation of Mo(CO)6.[2] Intermediate in inorganic and organometallic synthesisMo(CO)6 is a popular reagent in organometallic synthesis[3] because one or more CO ligands can be displaced by other donor ligands.[4] Mo(CO)6, [Mo(CO)3(MeCN)3], and related derivatives are employed as catalysts in organic synthesis for example, alkyne metathesis and the Pauson–Khand reaction. Mo(CO)6 reacts with 2,2′-bipyridine to afford Mo(CO)4(bipy). UV-photolysis of a THF solution of Mo(CO)6 gives Mo(CO)5(THF). [Mo(CO)4(piperidine)2]The thermal reaction of Mo(CO)6 with piperidine affords Mo(CO)4(piperidine)2. The two piperidine ligands in this yellow-colored compound are labile, which allows other ligands to be introduced under mild conditions. For instance, the reaction of [Mo(CO)4(piperidine)2] with triphenyl phosphine in boiling dichloromethane (b.p. ca. 40 °C) gives cis-[Mo(CO)4(PPh3)2]. This cis- complex isomerizes in toluene to trans-[Mo(CO)4(PPh3)2].[5] [Mo(CO)3(MeCN)3]Mo(CO)6 also can be converted to its tris(acetonitrile) derivative. The compound serves as a source of "Mo(CO)3". For instance treatment with allyl chloride gives [MoCl(allyl)(CO)2(MeCN)2], whereas treatment with KTp and sodium cyclopentadienide gives [MoTp(CO)3]− and [MoCp(CO)3]− anions, respectively. These anions react with a variety of electrophiles.[6] A related source of Mo(CO)3 is cycloheptatrienemolybdenum tricarbonyl. Source of Mo atomsMolybdenum hexacarbonyl is widely used in electron beam-induced deposition technique - it is easily vaporized and decomposed by the electron beam providing a convenient source of molybdenum atoms.[7] Safety and handlingLike all metal carbonyls, Mo(CO)6 is dangerous source of volatile metal as well as CO. It diffuses readily into plastic stoppers. References1. ^{{Cite web | title = Hexacarbonylmolybdenum (CHEBI:30508) | url = https://www.ebi.ac.uk/chebi/searchId.do?chebiId=30508 | work = Chemical Entities of Biological Interest (ChEBI) | location = UK | publisher = European Bioinformatics Institute }} 2. ^{{cite journal | last= Feldmann |first=J. | title = Determination of Ni(CO)4, Fe(CO)5, Mo(CO)6, and W(CO)6 in Sewage Gas by Using Cryotrapping Gas Chromatography Inductively Coupled Plasma Mass Spectrometry | journal = J. Environ. Monit. | year = 1999 | volume = 1 | issue = 1 | pages = 33–37 | doi = 10.1039/a807277i | pmid=11529076}} 3. ^{{ cite encyclopedia | last1= Faller |first1=J. W. |last2=Brummond |first2=K. M. |last3=Mitasev |first3=B. | title = Hexacarbonylmolybdenum | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | editor-first = L. |editor-last=Paquette | year = 2006 | publisher = J. Wiley & Sons | location = New York | doi = 10.1002/047084289X.rh004.pub2 }} 4. ^http://www.chm.bris.ac.uk/teaching-labs/inorganic2ndyear/2004-2005labmanual/Experiment3.pdf {{webarchive |url=https://web.archive.org/web/20080309162142/http://www.chm.bris.ac.uk/teaching-labs/inorganic2ndyear/2004-2005labmanual/Experiment3.pdf |date=March 9, 2008 }} 5. ^{{cite journal | last1 = Darensbourg | first1 = D. J. | last2 = Kump | first2 = R. L. | title = A Convenient Synthesis of cis-Mo(CO)4L2 Derivatives (L = Group 5a Ligand) and a Qualitative Study of Their Thermal Reactivity toward Ligand Dissociation |journal = Inorg. Chem. | year = 1978 | volume = 17 | issue = 9 | pages = 2680–2682 | doi = 10.1021/ic50187a062 }} 6. ^{{cite book | last1= Elschenbroich |first1=C. |last2=Salzer |first2=A. | title = Organometallics: A Concise Introduction | edition = 2nd | year = 1992 | publisher = Wiley-VCH | location = Weinheim | isbn = 3-527-28165-7 }} 7. ^{{ cite journal | last1 = Randolph | first1 = S. J. | last2 = Fowlkes | first2 = J. D. | last3 = Rack | first3 = P. D. | title = Focused, Nanoscale Electron-Beam-Induced Deposition and Etching | journal = Critical Reviews of Solid State and Materials Sciences | volume = 31 | year = 2006 | issue = 3 | pages = 55–89 | doi = 10.1080/10408430600930438 }} Further reading
3 : Molybdenum compounds|Carbonyl complexes|Octahedral compounds |
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