Ferrocenediyl-bridged triiron complexes

Lung Shiang Luh, Yuh Sheng Wen, Gyorgy Vanko, Ling Kang Liu

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Abstract

The reaction of 2 equiv of CpFe(CO)2I and 1,1′-dilithioferrocene in the presence of 2 equiv of PPh3 is an intermolecular version of the reaction of CpFe(CO)2I and (η5-C5H4Li)Fe (C5H4PPh2). In the three-component procedure, the PPh3 substitution for iodide on CpFe(CO)2I is much faster than the nucleophilic Fc-addition at the Fe-center or at a CO ligand of CpFe(CO)2I. This one-pot reaction proceeds through [CpFe(CO)2PPh3+] and yields CpFe(CO)(PPh3)- [μ,C:η5-C(O)C5H4 ]Fe[μ,η54-5-exo- (1′-C5H4)C5H5]Fe (CO)2(PPh3) (4) in 50% yield, with the 1,1′-dilithioferrocene participating twice in the nucleophilic Fc-additions: at the Cp-ring and at a CO ligand of [CpFe(CO)2PPh3+]. Complex 4 is a ferrocenediyl-bridged tri-Fe complex with three different Fe-centers: a metallocene Fe(II), a square-pyramidal pentacoordinate Fe(O), and a half-sandwich acyl-Fe(II). It has been found that, in the second Fc-additions, the pathway from (η5-C5H4Li)Fe[μ,η5: C-C5H4C(O)]FeCp(CO)(PPh3) (9) to 4 proceeds normally, but the pathway from 9 to Fe[(μ,η5: C-C5H4)C(O)FeCp(CO)(PPh3)]2 (5) has been turned off. The preference of Fc-addition of 9 onto the Cp-ring of [CpFe(CO)2PPh3+] could be reasoned by a localization of the Li+ cation in 9.

Original languageEnglish
Pages (from-to)2198-2206
Number of pages9
JournalOrganometallics
Volume20
Issue number11
DOIs
Publication statusPublished - May 28 2001

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Luh, L. S., Wen, Y. S., Vanko, G., & Liu, L. K. (2001). Ferrocenediyl-bridged triiron complexes. Organometallics, 20(11), 2198-2206. https://doi.org/10.1021/om0008528