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十甲基二茂鐵

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十甲基二茂鐵
IUPAC名
Decamethylferrocene
識別
CAS號 12126-50-0  checkY
PubChem 5148079
ChemSpider 4321548
SMILES
 
  • C[c-]1c(c(c(c1C)C)C)C.C[c-]1c(c(c(c1C)C)C)C.[Fe+2]
InChI
 
  • 1/2C10H15.Fe/c2*1-6-7(2)9(4)10(5)8(6)3;/h2*1-5H3;/q2*-1;+2
InChIKey SEYZDJPFVVXSRB-UHFFFAOYAP
性質
化學式 C20H30Fe
摩爾質量 326.3 g·mol−1
外觀 黃色晶體[1]
熔點 291-295 °C(564-568 K)([1]
升華條件 413 K, 5.3 Pa[2]
若非註明,所有數據均出自標準狀態(25 ℃,100 kPa)下。

十甲基二茂鐵,又稱雙(五甲基環五二烯)鐵(II),是一種有機化合物,化學式 Fe(C
5
(CH
3
)
5
)
2
或C
20
H
30
Fe。它是一種夾心配合物,由亞鐵離子(Fe2+)和兩個五甲基環戊二烯陰離子(Cp*-或(CH
3
)
5
C
5
)組成。它是二茂鐵的衍生物,由甲基取代所有的原子而成。十甲基二茂鐵有時簡寫為DmFc[3] Me
10
Fc [4]或FeCp*2[5]

十甲基二茂鐵是一種黃色晶體,是一種還原劑Fe(II)中心可以被輕易氧化成Fe(III),產生一價正離子十甲基二茂鐵(III)陽離子,甚至更高的氧化態。[6]

製備

十甲基二茂鐵可以由五甲基環戊二烯衍生物和氯化亞鐵反應而成:[7]

2 Li(C5Me5) + FeCl2 → Fe(C5Me5)2 + 2 LiCl

產物可以通過升華純化。鐵-碳平均距離約為 2.050 Å。它的結構已被X射線晶體學確認。[8]

反應

類似二茂鐵,十甲基二茂鐵的 Fe(II) 容易被氧化成 Fe(III)。由於十個甲基的誘導效應,十甲基二茂鐵的還原性比二茂鐵強。氧氣在十甲基二茂鐵的酸性溶液中會被還原成過氧化氫[9]

使用強氧化劑(例如SbF
5
或AsF
5
的SO
2
溶液,或是XeF+/Sb
2
F
11
的HF/SbF
5
溶液)氧化十甲基二茂鐵可以得到穩定的十甲基二茂鐵(IV)雙陽離子。在它的Sb
2
F
11
鹽中,兩個Cp環是平行的。相比之下,兩個Cp環在SbF
6
鹽中有17°的傾斜。[5]

參考資料

  1. ^ 1.0 1.1 King, R. B.; Bisnette, M. B. Organometallic Chemistry of the Transition Metals XXI. Some π-pentamethylcyclopentadienyl Derivatives of Various Transition Metals. J. Organomet. Chem. 1967, 8 (2): 287–297. doi:10.1016/S0022-328X(00)91042-8. 
  2. ^ Connelly, N.; Geiger, W. E. Chemical Redox Agents for Organometallic Chemistry. Chem. Rev. 1996, 96 (2): 877–910. PMID 11848774. doi:10.1021/cr940053x. 
  3. ^ Torriero, Angel A.J. Characterization of decamethylferrocene and ferrocene in ionic liquids: argon and vacuum effect on their electrochemical properties. Electrochimica Acta. 2014, 137: 235–244. doi:10.1016/j.electacta.2014.06.005. 
  4. ^ Noviandri, Indra; Brown, Kylie N.; Fleming, Douglas S.; Gulyas, Peter T.; Lay, Peter A.; Masters, Anthony F.; Phillips, Leonidas. 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. 1 August 1999, 103 (32): 6713–6722. ISSN 1520-6106. doi:10.1021/jp991381+. 
  5. ^ 5.0 5.1 Malischewski, M.; Adelhardt, M.; Sutter, J.; Meyer, K.; Seppelt, K. Isolation and structural and electronic characterization of salts of the decamethylferrocene dication. Science. 2016, 353 (6300): 678–682. Bibcode:2016Sci...353..678M. PMID 27516596. doi:10.1126/science.aaf6362. 
  6. ^ M. Malischewski, M. Adelhardt, J. Sutter, K. Meyer, K. Seppelt. Isolation and structural and electronic characterization of salts of the decamethylferrocene dication. Science. 2016-08-12, 353 (6300): 678–682 [2021-07-20]. ISSN 0036-8075. doi:10.1126/science.aaf6362 (英語). 
  7. ^ R.B. King, M.B. Bisnette: Organometallic chemistry of the transition metals XXI. Some π-pentamethylcyclopentadienyl derivatives of various transition metals. In: Journal of Organometallic Chemistry. 8, 1967, S. 287, doi:10.1016/S0022-328X(00)91042-8.
  8. ^ Freyberg, Derek P.; Robbins, John L.; Raymond, Kenneth N.; Smart, James C. Crystal and molecular structures of decamethylmanganocene and decamethylferrocene. Static Jahn-Teller distortion in a metallocene. J. Am. Chem. Soc. 1979, 101 (4): 892–897. doi:10.1021/ja00498a017. 
  9. ^ Su, Bin; Hatay, Imren; Ge, Pei Yu; Mendez, Manuel; Corminboeuf, Clemence; Samec, Zdenek; Ersoz, Mustafa; Girault, Hubert H. Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media. Chem. Commun. 2010, 46 (17): 2918–2919 [2021-07-18]. PMID 20386822. doi:10.1039/B926963K. (原始內容存檔於2020-06-12).