| 词条 | Disodium tetracarbonylferrate |
| 释义 |
| verifiedrevid = 449831753 | ImageFile = Disodium tetracarbonylferrate.png | ImageSize = | IUPACName = disodium tetracarbonylferrate | SystematicName = disodium tetracarbonylferrate | OtherNames = disodium iron tetracarbonyl, Collman's reagent |Section1={{Chembox Identifiers | Abbreviations = | CASNo_Ref = {{cascite|correct|??}} | CASNo = 14878-31-0 | EC_number = 238-951-0 | PubChem = 73357794 | SMILES = [CH-]=O.[CH-]=O.[CH-]=O.[CH-]=O.[Na+].[Na+].[Fe+2] | InChI=1S/4CHO.Fe.2Na/c4*1-2;;;/h4*1H;;;/q4*-1;+2;2*+1 | InChIKey = JSMIGIAJTPRDEQ-UHFFFAOYSA-N | RTECS = | MeSHName = | ChEBI_Ref = {{ebicite|correct|EBI}} | ChEBI = | KEGG_Ref = {{keggcite|correct|kegg}} | KEGG = }} |Section2={{Chembox Properties | Formula = C4FeNa2O4 | MolarMass = 213.87 | Appearance = Colorless solid | Density = 2.16 g/cm3, solid | MeltingPt = | MeltingPt_notes = | BoilingPt = | BoilingPt_notes = | Solubility = Decomposes | SolubleOther = tetrahydrofuran, dimethylformamide, dioxane | Solvent = | LogP = | VaporPressure = | HenryConstant = | AtmosphericOHRateConstant = | pKa = | pKb = }} |Section3={{Chembox Structure | CrystalStruct = Distorted tetrahedron | Coordination = Tetrahedral | MolShape = }} |Section7={{Chembox Hazards | EUClass = | MainHazards = Pyrophoric | NFPA-H = | NFPA-F = | NFPA-R = | NFPA-S = | RPhrases = | SPhrases = | RSPhrases = | FlashPt = | AutoignitionPt = | ExploLimits = | PEL = }} |Section8={{Chembox Related | OtherAnions = | OtherCations = | OtherFunction = | OtherFunction_label = | OtherCompounds = Iron pentacarbonyl}} }} Disodium tetracarbonylferrate is the organoiron compound with the formula Na2[Fe(CO)4]. It is always used as a solvate, e.g. with tetrahydrofuran or dimethoxyethane which bind to the sodium cation.[1] mainly to synthesise aldehydes.[2] This oxygen-sensitive colourless solid is a reagent in organometallic and organic chemical research but is not of commercial value. StructureThe dianion [Fe(CO)4]2− is isoelectronic with Ni(CO)4 and does adopt a tetrahedral structure in its salts. It is commonly used with dioxane complexed to the sodium cation, this dioxane solvate being known as Collman's reagent.[3] The tetracarbonylferrate dianion is tetrahedral.[4][5] SynthesisThe reagent was first prepared by reducing iron pentacarbonyl with sodium amalgam.[6] A more modern synthesis uses sodium naphthenide as the reducant. The efficiency of the synthesis depends on the quality of the iron pentacarbonyl.[1] Fe(CO)5 + 2 Na → Na2[Fe(CO)4] + CO When a deficiency of sodium is used, the reduction affords octacarbonyl diferrate:[1] 2 Fe(CO)5 + 2 Na → Na2[Fe2(CO)8] + 2 CO Other reducing agents work. Another way to synthesize Collman's Reagent is to use FeCl3.[7] FeCl3 + Na(C10H8) + 4CO + THF → +Na → Na2[Fe(CO)4] These synthesis pathways are extremely useful in preparing Collman's Reagent if the typical reagents to make it are not available.[8] ReactionsThe reagent was originally described for the conversion of primary alkyl bromides to the corresponding aldehydes in a two-step, "one-pot" reaction:[6] Na2[Fe(CO)4] + RBr → Na[RFe(CO)4] + NaBr This solution is then treated sequentially with PPh3 and then acetic acid to give the aldehyde, RCHO. Disodium tetracarbonylferrate can be used to convert acid chlorides to aldehydes. This reaction proceeds via the intermediacy of iron acyl complex. Na2[Fe(CO)4] + RCOCl → Na[RC(O)Fe(CO)4] + NaCl Na[RC(O)Fe(CO)4] + HCl → RCHO + "Fe(CO)4" + NaCl Disodium tetracarbonylferrate reacts with alkyl halides (RX) to produce alkyl complexes: Na2[Fe(CO)4] + RX → Na[RFe(CO)4] + NaX Such iron alkyls can be converted to the corresponding carboxylic acid and acid halides: Na[RFe(CO)4] + O2, H+ →→ RCO2H + Fe... Na[RFe(CO)4] + 2 X2 → RC(O)X + FeX2 + 3 CO + NaX References1. ^1 2 {{ cite journal |author1=Strong, H. |author2=Krusic, P. J. |author3=San Filippo, J. | title = Sodium Carbonyl Ferrates, Na2[Fe(CO)4], Na2[Fe2(CO)8], and Na2[Fe3(CO)11]. Bis[μ-Nitrido-Bis(triphenylphosphorus)1+] Undeca-Carbonyltriferrate2−, [(Ph3P)2N]2[Fe3(CO)11] | journal = Inorganic Syntheses | year = 1990 | volume = 28 | pages = 203–207 | isbn = 0-471-52619-3 | doi = 10.1002/9780470132593.ch52 | editor = R. J. Angelici | publisher = J. Wiley & Sons | location = New York }} 2. ^{{ cite encyclopedia | author = Pike, R. D. | title = Disodium Tetracarbonylferrate(-II) | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | year = 2001 | doi = 10.1002/047084289X.rd465 }} 3. ^{{ cite book |author1=Miessler, G. L. |author2=Tarr, D. A. | year = 2004 | title = Inorganic Chemistry | location = Upper Saddle River, NJ | publisher = Pearson }} 4. ^{{ cite journal |author1=Chin, H. B. |author2=Bau, R. | title = The Crystal Structure of Disodium Tetracarbonylferrate. Distortion of the Tetracarbonylferrate2− Anion in the Solid State | journal = Journal of the American Chemical Society | year = 1976 | volume = 98 | issue = 9 | pages = 2434–2439 | doi = 10.1021/ja00425a009 }} 5. ^{{cite journal|authors=Teller, R. G.; Finke, R. G.; Collman, J. P.; Chin, H. B.; Bau, R.|title=Dependence of the tetracarbonylferrate(2-) geometry on counterion: crystal structures of dipotassium tetracarbonylferrate and bis(sodium crypt) tetracarbonylferrate [crypt = N(CH2CH2OCH2CH2OCH2CH2)3N]|journal=Journal of the American Chemical Society|year=1977|volume=99|pages=1104-1111|doi=10.1021/ja00446a022}} 6. ^1 {{ cite journal | author = Cooke, M. P. | title = Facile Conversion of Alkyl Bromides into Aldehydes Using Sodium Tetracarbonylferrate(-II) | journal = Journal of the American Chemical Society | year = 1970 | volume = 92 | issue = 20 | pages = 6080–6082 | doi = 10.1021/ja00723a056 }} 7. ^1 {{ cite book | author = Scholsser, M. | year = 2013 | title = Organometallics in Synthesis, Third Manual | location = Chicester, England | publisher = Wiley }} 8. ^{{ cite book | author = Rameshkumar, C. | title = New Reactive Iron Carbonyl Reagents for Applications in Organic Synthesis | year = 2011 | location = Hyderabad, India | publisher = University of Hyderabad }} Further reading
3 : Carbonyl complexes|Iron compounds|Sodium compounds |
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