Destabilizing dπ-pπ orbital interactions and the alkylation reactions of iron(II)-thiolate complexes

Michael T. Ashby, John H. Enemark, Dennis L. Lichtenberger

Research output: Contribution to journalArticlepeer-review

102 Scopus citations


For CpFe(CO)2SR (1) (R = C6H4-p-Z; Z = OMe, H, Cl, CF3, NO2) the -type interaction between formally occupied metal d orbitals and the sulfur lone pair that is principally 3p in character has been modeled with Fenske-Hall molecular orbital calculations and experimentally investigated by gas-phase photoelectron spectroscopy. A calculation for 1 (R = H) predicts that the highest occupied molecular orbital (HOMO) is metal-sulfur antibonding and largely sulfur in character. The observed HOMO ionization energies of 1 correlate with several chemical properties, including the rate of reaction of the thiolate ligand with alkyl halides. Solvent and substituent effects on the reaction rate favor a mechanism involving nucleophilic displacement of the halide by the coordinated thiolate ligand. The nucleophilicity of the coordinated thiolate ligand of 1 is related to the metal-sulfur dπ-pπ antibonding interactions.

Original languageEnglish (US)
Pages (from-to)191-197
Number of pages7
JournalInorganic Chemistry
Issue number1
StatePublished - Jan 1 1988

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry


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