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Disodium tetracarbonylferrate
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<h2 id="structure">Structure</h2> <p>The dianion [Fe(CO)4]2− is isoelectronic with Ni(CO)4.<a class="footnote-ref" id="fnref:3" href="#fn:3"><sup>3</sup></a><a class="footnote-ref" id="fnref:4" href="#fn:4"><sup>4</sup></a> The iron center is tetrahedral, with Na+---OCFe interactions. It is commonly used with <a href="/facts/Dioxane/ILtQeBxC">dioxane</a> complexed to the sodium cation. </p> <h2 id="synthesis">Synthesis</h2> <p>The <a href="/facts/Reagent/c3GLInCu">reagent</a> was originally generated in situ by reducing <a href="/facts/Iron_pentacarbonyl/JzmkHzjX">iron pentacarbonyl</a> with sodium amalgam.<a class="footnote-ref" id="fnref:5" href="#fn:5"><sup>5</sup></a> Modern synthesis use <a href="/facts/Sodium_naphthalene/0MLBfHCS">sodium naphthalene</a> or sodium benzophenone ketyls as the reducants:<a class="footnote-ref" id="fnref:6" href="#fn:6"><sup>6</sup></a><a class="footnote-ref" id="fnref:7" href="#fn:7"><sup>7</sup></a> </p> Fe(CO)5 + 2 Na → Na2[Fe(CO)4] + CO <p>When a deficiency of sodium is used, the reduction affords deep yellow octacarbonyl <i>di</i>ferrate:<a class="footnote-ref" id="fnref:8" href="#fn:8"><sup>8</sup></a> </p> 2 Fe(CO)5 + 2 Na → Na2[Fe2(CO)8] + 2 CO <p>Some specialized methods do not start with iron carbonyl.<a class="footnote-ref" id="fnref:9" href="#fn:9"><sup>9</sup></a> </p> <h2 id="reactions">Reactions</h2> <p>It is used to synthesise <a href="/facts/Aldehyde/xSIRkW03">aldehydes</a> from alkyl halides.<a class="footnote-ref" id="fnref:10" href="#fn:10"><sup>10</sup></a> The reagent was originally described for the conversion of primary alkyl bromides to the corresponding aldehydes in a two-step, "one-pot" reaction:<a class="footnote-ref" id="fnref:11" href="#fn:11"><sup>11</sup></a> </p> Na2[Fe(CO)4] + RBr → Na[RFe(CO)4] + NaBr <p>This solution is then treated sequentially with <a href="/facts/Triphenylphosphine/nYFNCVcJ">PPh3</a> and then <a href="/facts/Acetic_acid/uyBKA2Pd">acetic acid</a> to give the aldehyde, RCHO. </p><p>Disodium tetracarbonylferrate can be used to convert <a href="/facts/Acyl_chloride/R4ppUXre">acyl chlorides</a> to aldehydes. This reaction proceeds via the intermediacy of iron <a href="/facts/Acyl/1vRPrmUX">acyl</a> complex. </p> Na2[Fe(CO)4] + RCOCl → Na[RC(O)Fe(CO)4] + NaCl Na[RC(O)Fe(CO)4] + <a href="/facts/Hydrogen_chloride/7Wzkhomd">HCl</a> → RCHO + "Fe(CO)4" + NaCl <p>Disodium tetracarbonylferrate reacts with <a href="/facts/Alkyl_halides/Enb7LQqt">alkyl halides</a> (RX) to produce alkyl complexes: </p> Na2[Fe(CO)4] + RX → Na[RFe(CO)4] + NaX <p>Such iron alkyls can be converted to the corresponding <a href="/facts/Carboxylic_acid/U4xuMosy">carboxylic acid</a> and <a href="/facts/Acid_halide/2EdXuvun">acid halides</a>: </p> Na[RFe(CO)4] + <a href="/facts/Oxygen/acyn6o8r">O2</a>, H+ →→ RCO2H + Fe... Na[RFe(CO)4] + 2 X2 → RC(O)X + FeX2 + 3 CO + NaX <h2 id="further-reading">Further reading</h2> <ul><li>Collman, J. P. (1975). "Disodium Tetracarbonylferrate, a Transition Metal Analog of a Grignard Reagent". <i><a href="/facts/Accounts_of_Chemical_Research/Vl0y5530">Accounts of Chemical Research</a></i>. 8 (10): 342–347. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1021%2Far50094a004">10.1021/ar50094a004</a>.</li> <li>Ungurenasu, C.; Cotzur, C. (1982). "Disodium Tetracarbonylferrate: A Reagent for Acid Functionalization of Halogenated Polymers". <i><a href="/facts/Polymer_Bulletin/tMHmKrrq">Polymer Bulletin</a></i>. 6 (5–6): 299–303. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1007%2FBF00255401">10.1007/BF00255401</a>. <a href="/facts/S2CID_(identifier)/ldJsHa2Y">S2CID</a> <a href="https://api.semanticscholar.org/CorpusID:101154955">101154955</a>.</li> <li>Hieber, V. W.; Braun, G. (1959). <a href="https://doi.org/10.1515%2Fznb-1959-0214">"Notizen: "Rheniumcarbonylwasserstoff" und Methylpentacarbonylrhenium"</a>. <i>Zeitschrift für Naturforschung B</i>. 14 (2): 132–133. <a href="/facts/Doi_(identifier)/muM9Etpq">doi</a>:<a href="https://doi.org/10.1515%2Fznb-1959-0214">10.1515/znb-1959-0214</a>. <a href="/facts/S2CID_(identifier)/ldJsHa2Y">S2CID</a> <a href="https://api.semanticscholar.org/CorpusID:94402946">94402946</a>.</li></ul> <h2 id="references">References</h2> <ol> <li id="fn:1"><p>Strong, H.; Krusic, P. J.; San Filippo, J. (1990). "Sodium Carbonyl Ferrates, Na 2 [Fe(Co) 4 ], Na 2 [Fe 2 (Co) 8 ], and Na 2 [Fe 3 (Co) 11 ]. Bis[ μ -Nitrido-Bis(Triphenylphosphorus)(1 +)] Undeca-Carbonyltriferrate(2-), [(Ph 3 P) 2 N] 2 [Fe 3 (Co) 11 ]". Inorganic Syntheses. Inorganic Syntheses. Vol. 28. pp. 203–207. doi:10.1002/9780470132593.ch52. ISBN 0-471-52619-3. <a href="0-471-52619-3" target="_blank">0-471-52619-3</a> <a href="#fnref:1" class="footnote-back-ref">↩</a></p></li> <li id="fn:2"><p>Miessler, G. L.; Tarr, D. A. (2004). Inorganic Chemistry. Upper Saddle River, NJ: Pearson. <a href="https://archive.org/details/inorganicchemist03edmies" target="_blank">https://archive.org/details/inorganicchemist03edmies</a> <a href="#fnref:2" class="footnote-back-ref">↩</a></p></li> <li id="fn:3"><p>Chin, H. B.; Bau, R. (1976). "The Crystal Structure of Disodium Tetracarbonylferrate. Distortion of the Tetracarbonylferrate2− Anion in the Solid State". Journal of the American Chemical Society. 98 (9): 2434–2439. doi:10.1021/ja00425a009. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:3" class="footnote-back-ref">↩</a></p></li> <li id="fn:4"><p>Teller, R. G.; Finke, R. G.; Collman, J. P.; Chin, H. B.; Bau, R. (1977). "Dependence of the tetracarbonylferrate(2-) geometry on counterion: crystal structures of dipotassium tetracarbonylferrate and bis(sodium crypt) tetracarbonylferrate [crypt = N(CH2CH2OCH2CH2OCH2CH2)3N]". Journal of the American Chemical Society. 99 (4): 1104–1111. doi:10.1021/ja00446a022. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:4" class="footnote-back-ref">↩</a></p></li> <li id="fn:5"><p>Cooke, M. P. (1970). "Facile Conversion of Alkyl Bromides into Aldehydes Using Sodium Tetracarbonylferrate(-II)". Journal of the American Chemical Society. 92 (20): 6080–6082. doi:10.1021/ja00723a056. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:5" class="footnote-back-ref">↩</a></p></li> <li id="fn:6"><p>Strong, H.; Krusic, P. J.; San Filippo, J. (1990). "Sodium Carbonyl Ferrates, Na 2 [Fe(Co) 4 ], Na 2 [Fe 2 (Co) 8 ], and Na 2 [Fe 3 (Co) 11 ]. Bis[ μ -Nitrido-Bis(Triphenylphosphorus)(1 +)] Undeca-Carbonyltriferrate(2-), [(Ph 3 P) 2 N] 2 [Fe 3 (Co) 11 ]". Inorganic Syntheses. Inorganic Syntheses. Vol. 28. pp. 203–207. doi:10.1002/9780470132593.ch52. ISBN 0-471-52619-3. <a href="0-471-52619-3" target="_blank">0-471-52619-3</a> <a href="#fnref:6" class="footnote-back-ref">↩</a></p></li> <li id="fn:7"><p>Richard G. Finke, Thomas N. Sorrell (1979). "Nucleophilic Acylation with Disodium Tetracarbonylferrate: Methyl 7-Oxoheptanoate and Methyl 7-Oxoöctanoate". Organic Syntheses. 59: 102. doi:10.15227/orgsyn.059.0102. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:7" class="footnote-back-ref">↩</a></p></li> <li id="fn:8"><p>Strong, H.; Krusic, P. J.; San Filippo, J. (1990). "Sodium Carbonyl Ferrates, Na 2 [Fe(Co) 4 ], Na 2 [Fe 2 (Co) 8 ], and Na 2 [Fe 3 (Co) 11 ]. Bis[ μ -Nitrido-Bis(Triphenylphosphorus)(1 +)] Undeca-Carbonyltriferrate(2-), [(Ph 3 P) 2 N] 2 [Fe 3 (Co) 11 ]". Inorganic Syntheses. Inorganic Syntheses. Vol. 28. pp. 203–207. doi:10.1002/9780470132593.ch52. ISBN 0-471-52619-3. <a href="0-471-52619-3" target="_blank">0-471-52619-3</a> <a href="#fnref:8" class="footnote-back-ref">↩</a></p></li> <li id="fn:9"><p>Scholsser, M. (2013). Organometallics in Synthesis, Third Manual. Chicester, England: Wiley. <a href="#fnref:9" class="footnote-back-ref">↩</a></p></li> <li id="fn:10"><p>Pike, R. D. (2001). "Disodium Tetracarbonylferrate(-II)". Encyclopedia of Reagents for Organic Synthesis. doi:10.1002/047084289X.rd465. <a href="/wiki/Doi_(identifier)" target="_blank">/wiki/Doi_(identifier)</a> <a href="#fnref:10" class="footnote-back-ref">↩</a></p></li> <li id="fn:11"><p>Cooke, M. P. (1970). "Facile Conversion of Alkyl Bromides into Aldehydes Using Sodium Tetracarbonylferrate(-II)". Journal of the American Chemical Society. 92 (20): 6080–6082. doi:10.1021/ja00723a056. <a href="/wiki/Journal_of_the_American_Chemical_Society" target="_blank">/wiki/Journal_of_the_American_Chemical_Society</a> <a href="#fnref:11" class="footnote-back-ref">↩</a></p></li> </ol>