This compound is a yellow crystalline solid that is used in chemical laboratories as a weak reductant. The iron(II) core is easily oxidized to iron(III), yielding the monovalent cation decamethylferrocenium, and even to higher oxidation states.[5]
Preparationedit
Decamethylferrocene is prepared in the same manner as ferrocene from pentamethylcyclopentadiene. This method can be used to produce other decamethylcyclopentadienyl sandwich compounds.[1]
2 Li(C5Me5) + FeCl2 → Fe(C5Me5)2 + 2 LiCl
The product can be purified by sublimation. FeCp*2 has staggered Cp* rings. The average distance between iron and each carbon is approximately 2.050 Å. This structure has been confirmed by X-ray crystallography.[6]
Redox reactionsedit
Like ferrocene, decamethylferrocene forms a stable cation because Fe(II) is easily oxidized to Fe(III). Because of the electron donating methyl groups on the Cp* groups, decamethylferrocene is more reducing than is ferrocene. In a solution of acetonitrile the reduction potential for the [FeCp*2]+/0 couple is −0.59 V compared to a [FeCp2]0/+ reference (−0.48 V vs Fc/Fc+ in CH2Cl2).[2] Oxygen is reduced to hydrogen peroxide by decamethylferrocene in acidic solution.[7]
Using powerful oxidants (e.g. SbF5 or AsF5 in SO2, or XeF+/Sb2F−11 in HF/SbF5) decamethylferrocene is oxidized to a stable dication with an iron(IV) core. In the Sb2F−11 salt, the Cp* rings are parallel. In contrast, a tilt angle of 17° between the Cp* rings is observed in the crystal structure of the SbF−6 salt.[5]
Referencesedit
^ abcKing, R. B.; Bisnette, M. B. (1967). "Organometallic Chemistry of the Transition Metals XXI. Some π-pentamethylcyclopentadienyl Derivatives of Various Transition Metals". J. Organomet. Chem.8 (2): 287–297. doi:10.1016/S0022-328X(00)91042-8.
^ abConnelly, N.; Geiger, W. E. (1996). "Chemical Redox Agents for Organometallic Chemistry". Chem. Rev.96 (2): 877–910. doi:10.1021/cr940053x. PMID 11848774.
^Torriero, Angel A. J. (2014). "Characterization of decamethylferrocene and ferrocene in ionic liquids: argon and vacuum effect on their electrochemical properties". Electrochimica Acta. 137: 235–244. doi:10.1016/j.electacta.2014.06.005.
^Noviandri, Indra; Brown, Kylie N.; Fleming, Douglas S.; Gulyas, Peter T.; Lay, Peter A.; Masters, Anthony F.; Phillips, Leonidas (1 August 1999). "The Decamethylferrocenium/Decamethylferrocene Redox Couple: A Superior Redox Standard to the Ferrocenium/Ferrocene Redox Couple for Studying Solvent Effects on the Thermodynamics of Electron Transfer". The Journal of Physical Chemistry B. 103 (32): 6713–6722. doi:10.1021/jp991381+. ISSN 1520-6106.
^ abcMalischewski, M.; Adelhardt, M.; Sutter, J.; Meyer, K.; Seppelt, K. (2016). "Isolation and structural and electronic characterization of salts of the decamethylferrocene dication". Science. 353 (6300): 678–682. Bibcode:2016Sci...353..678M. doi:10.1126/science.aaf6362. PMID 27516596. S2CID 43385610.
^Freyberg, Derek P.; Robbins, John L.; Raymond, Kenneth N.; Smart, James C. (1979). "Crystal and molecular structures of decamethylmanganocene and decamethylferrocene. Static Jahn-Teller distortion in a metallocene". J. Am. Chem. Soc.101 (4): 892–897. doi:10.1021/ja00498a017.
^Su, Bin; Hatay, Imren; Ge, Pei Yu; Mendez, Manuel; Corminboeuf, Clemence; Samec, Zdenek; Ersoz, Mustafa; Girault, Hubert H. (2010). "Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media". Chem. Commun.46 (17): 2918–2919. doi:10.1039/B926963K. PMID 20386822.
April 12, 2024
decamethylferrocene, pentamethylcyclopentadienyl, iron, chemical, compound, with, formula, c20h30fe, sandwich, compound, whose, molecule, iron, cation, attached, coordination, bonds, between, pentamethylcyclopentadienyl, anions, also, viewed, derivative, ferro. Decamethylferrocene or bis pentamethylcyclopentadienyl iron II is a chemical compound with formula Fe C5 CH3 5 2 or C20H30Fe It is a sandwich compound whose molecule has an iron II cation Fe2 attached by coordination bonds between two pentamethylcyclopentadienyl anions Cp CH3 5C 5 It can also be viewed as a derivative of ferrocene with a methyl group replacing each hydrogen atom of its cyclopentadienyl rings The name and formula are often abbreviated to DmFc 3 Me10Fc 4 or FeCp 2 5 Decamethylferrocene NamesPreferred IUPAC name DecamethylferroceneOther names Bis h5 pentamethylcyclopentadienyl iron II Decamethyl ferrocene1 1 2 2 3 3 4 4 5 5 Decamethyl ferroceneBis pentamethylcyclopentadienyl iron II PermethylferroceneIdentifiersCAS Number 12126 50 0 Y3D model JSmol Interactive imageChemSpider 4321548 NECHA InfoCard 100 116 086PubChem CID 5148079CompTox Dashboard EPA DTXSID80923743InChI InChI 1S 2C10H15 Fe c2 1 6 7 2 9 4 10 5 8 6 3 h2 1 5H3 q2 1 2 NKey SEYZDJPFVVXSRB UHFFFAOYSA N NInChI 1 2C10H15 Fe c2 1 6 7 2 9 4 10 5 8 6 3 h2 1 5H3 q2 1 2Key SEYZDJPFVVXSRB UHFFFAOYAPSMILES C c 1c c c c1C C C C C c 1c c c c1C C C C Fe 2 PropertiesChemical formula C 20H 30FeMolar mass 326 305 g mol 1Appearance Yellow crystalline solid 1 Melting point 291 to 295 C 556 to 563 F 564 to 568 K 1 Sublimationconditions 413 K 5 3 Pa 2 Except where otherwise noted data are given for materials in their standard state at 25 C 77 F 100 kPa N verify what is Y N Infobox references This compound is a yellow crystalline solid that is used in chemical laboratories as a weak reductant The iron II core is easily oxidized to iron III yielding the monovalent cation decamethylferrocenium and even to higher oxidation states 5 Preparation editDecamethylferrocene is prepared in the same manner as ferrocene from pentamethylcyclopentadiene This method can be used to produce other decamethylcyclopentadienyl sandwich compounds 1 2 Li C5Me5 FeCl2 Fe C5Me5 2 2 LiClThe product can be purified by sublimation FeCp 2 has staggered Cp rings The average distance between iron and each carbon is approximately 2 050 A This structure has been confirmed by X ray crystallography 6 Redox reactions editLike ferrocene decamethylferrocene forms a stable cation because Fe II is easily oxidized to Fe III Because of the electron donating methyl groups on the Cp groups decamethylferrocene is more reducing than is ferrocene In a solution of acetonitrile the reduction potential for the FeCp 2 0 couple is 0 59 V compared to a FeCp2 0 reference 0 48 V vs Fc Fc in CH2Cl2 2 Oxygen is reduced to hydrogen peroxide by decamethylferrocene in acidic solution 7 Using powerful oxidants e g SbF5 or AsF5 in SO2 or XeF Sb2F 11 in HF SbF5 decamethylferrocene is oxidized to a stable dication with an iron IV core In the Sb2F 11 salt the Cp rings are parallel In contrast a tilt angle of 17 between the Cp rings is observed in the crystal structure of the SbF 6 salt 5 References edit a b c King R B Bisnette M B 1967 Organometallic Chemistry of the Transition Metals XXI Some p pentamethylcyclopentadienyl Derivatives of Various Transition Metals J Organomet Chem 8 2 287 297 doi 10 1016 S0022 328X 00 91042 8 a b Connelly N Geiger W E 1996 Chemical Redox Agents for Organometallic Chemistry Chem Rev 96 2 877 910 doi 10 1021 cr940053x PMID 11848774 Torriero Angel A J 2014 Characterization of decamethylferrocene and ferrocene in ionic liquids argon and vacuum effect on their electrochemical properties Electrochimica Acta 137 235 244 doi 10 1016 j electacta 2014 06 005 Noviandri Indra Brown Kylie N Fleming Douglas S Gulyas Peter T Lay Peter A Masters Anthony F Phillips Leonidas 1 August 1999 The Decamethylferrocenium Decamethylferrocene Redox Couple A Superior Redox Standard to the Ferrocenium Ferrocene Redox Couple for Studying Solvent Effects on the Thermodynamics of Electron Transfer The Journal of Physical Chemistry B 103 32 6713 6722 doi 10 1021 jp991381 ISSN 1520 6106 a b c Malischewski M Adelhardt M Sutter J Meyer K Seppelt K 2016 Isolation and structural and electronic characterization of salts of the decamethylferrocene dication Science 353 6300 678 682 Bibcode 2016Sci 353 678M doi 10 1126 science aaf6362 PMID 27516596 S2CID 43385610 Freyberg Derek P Robbins John L Raymond Kenneth N Smart James C 1979 Crystal and molecular structures of decamethylmanganocene and decamethylferrocene Static Jahn Teller distortion in a metallocene J Am Chem Soc 101 4 892 897 doi 10 1021 ja00498a017 Su Bin Hatay Imren Ge Pei Yu Mendez Manuel Corminboeuf Clemence Samec Zdenek Ersoz Mustafa Girault Hubert H 2010 Oxygen and proton reduction by decamethylferrocene in non aqueous acidic media Chem Commun 46 17 2918 2919 doi 10 1039 B926963K PMID 20386822 Retrieved from https en wikipedia org w index php title Decamethylferrocene amp oldid 1091576705, wikipedia, wiki, book, books, library,
