Tertiary phosphine induced migratory carbonyl insertion in cyclopentadienyl complexes of iron(II)

Ntaoleng M. Makunya, Reinout Meijboom, Alfred Muller, Andreas Roodt

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11 Citations (Scopus)


Cyclopentadienyldicarbonylmethyliron, [CpFe(CO)2Me] (1), undergoes migratory carbonyl insertion under the influence of isosteric phosphine ligands P(4-FC6H4)3 and P(4-MeC 6H4)3. The products of the reaction, [CpFe(CO)(COMe)P(4-FC6H4)3] (2a) and [CpFe(CO)(COMe)P(4-MeC6H4)3] (2b), were characterised by X-ray crystallography. In both structures, the iron atom adopts a pseudo octahedral coordination geometry. Fe-P bond distances are the same at 2.1932(8) Å in 2a and 2b, respectively. Thus, contrary to what was expected, X-ray data could not be used to quantitatively differentiate between the two phosphine ligands in 2a and 2b. Therefore, additional spectroscopic techniques such as IR and NMR were employed. Similarly, the Fe-C bond lengths of the carbonyl (Fe-CO) and acetyl (Fe-COMe) are 1.748(3) and 1.955(3) in 2a, and 1.744(3) and 1.951(3) Å in 2b, respectively. The migratory carbonyl insertion was studied by NMR, IR, and UV-vis spectroscopies to determine the mechanism and the rate law. Results from NMR spectroscopy show that the formation of the product is accompanied by oxidation of the corresponding phosphine ligand. An increase in the reactivity of migratory carbonyl insertion for P(4-MeC6H4)3 was observed when the solvent was changed from CH2Cl2 to MeCN. The kinetic data showed that P(4-MeC6H4)3 reacts faster than P(4-FC6H4)3.

Original languageEnglish
Pages (from-to)4159-4167
Number of pages9
JournalJournal of Organometallic Chemistry
Issue number18
Publication statusPublished - 15 Sept 2005
Externally publishedYes


  • Iron
  • Kinetics
  • Migratory carbonyl insertion
  • X-ray crystallography

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry


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