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{{chembox {{chembox
| verifiedrevid = 437321725 |verifiedrevid = 449831753
| ImageFile = Disodium tetracarbonylferrate.png |ImageFile = Disodium tetracarbonylferrate.png
|IUPACName = disodium tetracarbonylferrate
| ImageSize =
| IUPACName = disodium tetracarbonylferrate |SystematicName = disodium tetracarbonylferrate
| SystematicName = disodium tetracarbonylferrate |OtherNames = disodium iron tetracarbonyl,
| OtherNames = disodium iron tetracarbonyl,
Collman's reagent Collman's reagent
| Section1 = {{Chembox Identifiers |Section1={{Chembox Identifiers
| Abbreviations = |Abbreviations =
|CASNo_Ref = {{cascite|correct|??}}
| CASNo = 14878-31-0
|CASNo = 14878-31-0
| EINECS =
|EC_number = 238-951-0
| EINECSCASNO =
| PubChem = |PubChem = 73357794
|SMILES = ..#(#)(#)#
| SMILES =
|InChI=1S/4CHO.Fe.2Na/c4*1-2;;;/h4*1H;;;/q4*-1;+2;2*+1
| InChI =
|InChIKey = JSMIGIAJTPRDEQ-UHFFFAOYSA-N
| RTECS =
| MeSHName =
| ChEBI_Ref = {{ebicite|correct|EBI}}
| ChEBI =
| KEGG_Ref = {{keggcite|correct|kegg}}
| KEGG =
| ATCCode_prefix =
| ATCCode_suffix =
| ATC_Supplemental =}}
| Section2 = {{Chembox Properties
| Formula = C<sub>4</sub>FeNa<sub>2</sub>O<sub>4</sub>
| MolarMass = 213.87
| Appearance = Colorless solid
| Density = 2.16 g/cm<sup>3</sup>, solid
| MeltingPt =
| Melting_notes =
| BoilingPt =
| Boiling_notes =
| Solubility = Decomposes
| SolubleOther = ], ], ]
| Solvent =
| LogP =
| VaporPressure =
| HenryConstant =
| AtmosphericOHRateConstant =
| pKa =
| pKb = }}
| Section3 = {{Chembox Structure
| CrystalStruct = Distorted tetrahedron
| Coordination = Tetrahedral
| MolShape = }}
| Section7 = {{Chembox Hazards
| EUClass =
| EUIndex =
| MainHazards = ]
| NFPA-H =
| NFPA-F =
| NFPA-R =
| NFPA-O =
| RPhrases =
| SPhrases =
| RSPhrases =
| FlashPt =
| Autoignition =
| ExploLimits =
| PEL = }}
| Section8 = {{Chembox Related
| OtherAnions =
| OtherCations =
| OtherFunctn =
| Function =
| OtherCpds = ]}}
}} }}
|Section2={{Chembox Properties
'''Disodium tetracarbonylferrate''' is the ] with the formula Na<sub>2</sub>. This ]-sensitive colourless solid is employed in ]",<ref name = RJA>{{cite journal | author = Strong, H.; Krusic, P. J.; San Filippo, J. | title = Sodium Carbonyl Ferrate, Na<sub>2</sub>Fe(CO)], Na<sub>2</sub>, and Na<sub>2</sub>. Bis Undecarcarbonyltriferrate(2-), <sub>2</sub> | journal = ] | year = 1990 | volume = 28 | pages = 203–207 | isbn = 0-471-52619-3 | doi = 10.1002/9780470132593.ch52 | editor = Robert J. Angelici | publisher = J. Wiley & Sons | location = New York | series = Inorganic Syntheses}}</ref> mainly to synthesise ]s.<ref>Pike, Robert D., (2001). Disodium Tetracarbonylferrate (II-). ''Encyclopedia of Reagents for Organic Synthesis.''</ref> It is commonly used with ] complexed to the sodium cation, this dioxane solvate being known as ] reagent.<ref> Miessler, G. L., Tarr, D. A. (2004). ''Inorganic chemistry.'' Upper Saddle River,New Jersey: Pearson Publication.</ref> The tetracarbonylferrate dianion is tetrahedral.<ref>{{cite journal
|Formula = C<sub>4</sub>FeNa<sub>2</sub>O<sub>4</sub>
| author = H. B. Chin, R. Bau
|MolarMass = 213.87
| year = 1976
|Appearance = Colorless solid
| title = The Crystal Structure of Disodium Tetracarbonylferrate. Distortion of the Tetracarbonylferrate(2-) Anion in the Solid State
|Density = 2.16 g/cm<sup>3</sup>, solid
| journal = ]
|Solubility = Decomposes
| volume = 98
|SolubleOther = ], ], ]
| pages = 2434–2439
}}
| doi = 10.1021/ja00425a009
|Section3={{Chembox Structure
| issue = 9
|CrystalStruct = Distorted tetrahedron
}}</ref>
|Coordination = Tetrahedral
}}
|Section7={{Chembox Hazards
|MainHazards = ]
}}
|Section8={{Chembox Related
|OtherCompounds = ]}}
}}
'''Disodium tetracarbonylferrate''' is the ] with the formula Na<sub>2</sub>. It is always used as a solvate, e.g., with ] or ], which bind to the sodium cation.<ref name = RJA>{{cite book |author1=Strong, H.|author2=Krusic, P. J. |author3=San Filippo, J. |chapter=Sodium Carbonyl Ferrates, Na <sub>2</sub> &#91;Fe(Co) <sub>4</sub> &#93;, Na <sub>2</sub> &#91;Fe <sub>2</sub> (Co) <sub>8</sub> &#93;, and Na <sub>2</sub> &#91;Fe <sub>3</sub> (Co) <sub>11</sub> &#93;. Bis&#91; ''μ'' -Nitrido-Bis(Triphenylphosphorus)(1 +)&#93; Undeca-Carbonyltriferrate(2-), &#91;(Ph <sub>3</sub> P) <sub>2</sub> N&#93; <sub>2</sub> &#91;Fe <sub>3</sub> (Co) <sub>11</sub> &#93; | title = Inorganic Syntheses | series = ] | year = 1990 | volume = 28 | pages = 203–207 | isbn = 0-471-52619-3 | doi = 10.1002/9780470132593.ch52}}</ref> An ]-sensitive colourless solid, it is a reagent in organometallic and organic chemical research. The dioxane solvated sodium salt is known as '''Collman's reagent''', in recognition of ], an early popularizer of its use.<ref>{{cite book |author1=Miessler, G. L. |author2=Tarr, D. A. | year = 2004 | title = Inorganic Chemistry |url=https://archive.org/details/inorganicchemist03edmies |url-access=registration | location = Upper Saddle River, NJ | publisher = Pearson}}</ref>

==Structure==
The dianion <sup>2−</sup> is isoelectronic with Ni(CO)<sub>4</sub>.<ref>{{ cite journal |author1=Chin, H. B. |author2=Bau, R. | title = The Crystal Structure of Disodium Tetracarbonylferrate. Distortion of the Tetracarbonylferrate<sup>2−</sup> Anion in the Solid State | journal = ] | year = 1976 | volume = 98 | issue = 9 | pages = 2434–2439 | doi = 10.1021/ja00425a009 }}</ref><ref>{{cite journal|author1=Teller, R. G. |author2=Finke, R. G. |author3=Collman, J. P. |author4=Chin, H. B. |author5=Bau, R. |title=Dependence of the tetracarbonylferrate(2-) geometry on counterion: crystal structures of dipotassium tetracarbonylferrate and bis(sodium crypt) tetracarbonylferrate |journal=Journal of the American Chemical Society|year=1977|volume=99|issue = 4|pages=1104–1111|doi=10.1021/ja00446a022}}</ref> The iron center is tetrahedral, with Na<sup>+</sup>---OCFe interactions. It is commonly used with ] complexed to the sodium cation.


==Synthesis== ==Synthesis==
The ] was reported by Cooke in 1970.<ref name=Cooke>{{cite journal | author = M. P. Cooke | title = Facile conversion of alkyl bromides into aldehydes using sodium tetracarbonylferrate(-II) | year = 1970 | journal = ] | volume = 92 | issue = 20 | pages = 6080–6082 | doi = 10.1021/ja00723a056}}</ref> The current synthesis entails the reduction of a solution of ] in ] by ]. The efficiency of the synthesis depends on the quality of the iron pentacarbonyl.<ref name = RJA/> The ] was originally generated in situ by reducing ] with sodium amalgam.<ref name=Cooke>{{ cite journal | author = Cooke, M. P. | title = Facile Conversion of Alkyl Bromides into Aldehydes Using Sodium Tetracarbonylferrate(-II) | journal = ] | year = 1970 | volume = 92 | issue = 20 | pages = 6080–6082 | doi = 10.1021/ja00723a056 }}</ref> Modern synthesis use ] or sodium benzophenone ketyls as the reducants:<ref name = RJA/><ref>{{cite journal |author=Richard G. Finke, Thomas N. Sorrell|doi=10.15227/orgsyn.059.0102|title=Nucleophilic Acylation with Disodium Tetracarbonylferrate: Methyl 7-Oxoheptanoate and Methyl 7-Oxoöctanoate|journal=Organic Syntheses|year=1979|volume=59|page=102}}</ref>
:Fe(CO)<sub>5</sub> + 2 ] → Na<sub>2</sub> + ] :Fe(CO)<sub>5</sub> + 2 Na → Na<sub>2</sub> + CO

When a deficiency of sodium is used, the reduction affords deep yellow octacarbonyl ''di''ferrate:<ref name = RJA/>
:2 Fe(CO)<sub>5</sub> + 2 Na → Na<sub>2</sub> + 2 CO
Some specialized methods do not start with iron carbonyl.<ref name="ref1">{{ cite book | author = Scholsser, M. | year = 2013 | title = Organometallics in Synthesis, Third Manual | location = Chicester, England | publisher = Wiley }}</ref>


==Reactions== ==Reactions==
It is used to synthesise ]s from alkyl halides.<ref>{{ cite encyclopedia | author = Pike, R. D. | title = Disodium Tetracarbonylferrate(-II) | encyclopedia = Encyclopedia of Reagents for Organic Synthesis | year = 2001 | doi = 10.1002/047084289X.rd465 }}</ref>
The reagent was originally described for the conversion of primary alkyl bromides, RBr, to the corresponding aldehydes in a two-step, "one-pot" reaction:<ref name=Cooke/>
The reagent was originally described for the conversion of primary alkyl bromides to the corresponding aldehydes in a two-step, "one-pot" reaction:<ref name=Cooke/>
:Na<sub>2</sub> + RBr → Na + ]
:Na<sub>2</sub> + RBr → Na + NaBr
This solution is then treated sequentially with ] and then ] to give the aldehyde, RCHO. This solution is then treated sequentially with ] and then ] to give the aldehyde, RCHO.


Disodium tetracarbonylferrate can be used to convert ]s to aldehydes. As for Cooke’s early discovery, an iron ] complex undergoes protonolysis to give the aldehyde. Disodium tetracarbonylferrate can be used to convert ]s to aldehydes. This reaction proceeds via the intermediacy of iron ] complex.
:Na<sub>2</sub> + RCOCl → Na + NaCl :Na<sub>2</sub> + RCOCl → Na + NaCl
:Na + ] → RCHO + "Fe(CO)<sub>4</sub>" + NaCl :Na + ] → RCHO + "Fe(CO)<sub>4</sub>" + NaCl
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Such iron alkyls can be converted to the corresponding ] and ]s: Such iron alkyls can be converted to the corresponding ] and ]s:
:Na + ], H<sup>+</sup> →→ RCO<sub>2</sub>H + Fe... :Na + ], H<sup>+</sup> →→ RCO<sub>2</sub>H + Fe...
:Na + X<sub>2</sub> → RC(O)X + FeX<sub>2</sub> + 3 CO + NaCl :Na + 2 X<sub>2</sub> → RC(O)X + FeX<sub>2</sub> + 3 CO + NaX

<!-- Lithium (or CO) can be added to form the complex Na, then R<sup>'</sup>X can be added to form RC(O)R<sup>'</sup>.<ref name="ref1"></ref>


:Na + L → Na → RC(O)R<sup>'</sup> + Na-->
One attraction of these methods is the low cost of the iron carbonyl as well as the fact that the procedures are relatively “green” because the side product is iron-based.
==References== ==References==
{{reflist}} {{reflist}}


==Further reading== ==Further reading==
* {{ cite journal | author = Collman, J. P. | title = Disodium Tetracarbonylferrate, a Transition Metal Analog of a Grignard Reagent | journal = ] | year = 1975 | volume = 8 | issue = 10 | pages = 342–347 | doi = 10.1021/ar50094a004 }}
*{{cite journal
* {{ cite journal |author1=Ungurenasu, C. |author2=Cotzur, C. | title = Disodium Tetracarbonylferrate: A Reagent for Acid Functionalization of Halogenated Polymers | journal = ] | year = 1982 | volume = 6 | issue = 5–6 | pages = 299–303 | doi = 10.1007/BF00255401 |s2cid=101154955 }}
| author = J. P. Collman
* {{ cite journal |author1=Hieber, V. W. |author2=Braun, G. | title = Notizen: "Rheniumcarbonylwasserstoff" und Methylpentacarbonylrhenium| journal = Zeitschrift für Naturforschung B | year = 1959 | volume = 14 |issue=2 | pages = 132–133 | doi = 10.1515/znb-1959-0214|s2cid=94402946 | doi-access = free }}
| year = 1975
| title = Disodium Tetracarbonylferrate, a Transition Metal Analog of a ]
| journal = ]
| volume = 8
| pages = 342–347
| doi = 10.1021/ar50094a004
| issue = 10
}}
*{{cite journal
| author = C. Ungurenasu, C. Cotzur
| year = 1982
| title = Disodium Tetracarbonylferrate: A Reagent for Acid Functionalization of Halogenated Polymers
| journal = ]
| volume = 6
| pages = 299–303
| doi = 10.1007/BF00255401
| issue = 5–6
}}
*{{cite journal
| author = V. W. Hieber, G. Braun
| year = 1959
| title =
| journal = ]
| volume = 146
| pages = 132
| doi =
}}


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