Displacement of Acetone from η-(C₅R₅)(CO)Fe(AC)(COMe)+ by Thioethers. Application of the Quantitative Analysis of Ligand Effects (QALE)

Authors

Anthony L. Fernandez, Merrimack CollegeFollow
Alfred Prock
Warren P. Giering

Document Type

Article - Merrimack Access Only

Publication Title

Organometallics

Publisher

American Chemical Society

Publication Date

6-1996

Abstract/ Summary

The displacement of acetone (AC) from η-(C₅R₅)(CO)Fe(AC)(COMe)⁺ (R = H, Me) by thioethers {SMe₂, SMeEt, SEt₂, S(n-Bu₂), SMe(t-Bu), S(i-Pr)₂,S(t-Bu)₂, SPh₂, SMe(p-XC₆H₄) (X = H, Me, MeO, Cl), and SEtPh} at −41 °C was studied using square-wave voltammetry. Rate constants were extracted from the square-wave voltammograms using computer simulation methods and were found to be sensitive to the stereoelectronic properties of the nucleophiles. The Cp (C₅H₅) complex is more reactive toward the smaller thioethers than the Cp* (C₅Me₅) complex, but there is an inversion of reactivity for the large thioethers. The rate constants were analyzed in terms of the electronic parameters (χ and E_ar) and one of the steric parameters θ, E_R, or Ω_s. The best correlation is found using χ, θ, and Ear. Of the two families of complexes, the rates of reaction of the Cp* complex with the thioethers are lessdependent on the stereoelectronic properties of the nucleophiles. This leads to a model of the transition states for the Cp* complex that is more flexible than that for the Cp complex, thereby allowing the reactions with the larger thioethers.

Repository Citation

Fernandez, A. L., Prock, A., & Giering, W. P. (1996). Displacement of Acetone from η-(C₅R₅)(CO)Fe(AC)(COMe)+ by Thioethers. Application of the Quantitative Analysis of Ligand Effects (QALE). Organometallics, 15(12), 2784-2789.
Available at: https://scholarworks.merrimack.edu/chm_facpub/9