Reactivity of the CpMn(CO)2−XR Bond [X = Cl, Br]: A Kinetic Study Using Rapid-Scan FTIR Spectroscopy Academic Article uri icon


  • The mechanism and energetics of the displacement of dihaloalkanes from the photolytically generated CpMn(CO)2-XR (X = Cl, Br) complexes by 2,6-lutidine have been studied using rapid-scan FTIR. The substitution reactions proceed through an Id mechanism, and theoretical calculations indicate that the Mn-XR bond is mostly broken in the transition state. Activation enthalpies of 16-17 kcal/mol for the Mn-ClR and 18-19 kcal/mol for the Mn-BrR complexes are only slightly lower than previous thermodynamic measurements of the Mn-haloalkane bond dissociation enthalpies. The rate of displacement of bromoalkanes was found to be ∼10 times slower than for the analogous chloroalkanes. Ab initio calculations suggest that this difference in reactivity is primarily due to a more stable interaction between the Mn center and bromoalkanes. © 2008 American Chemical Society.

published proceedings

  • Organometallics

author list (cited authors)

  • Bengali, A. A., & Fan, W. Y

citation count

  • 8

complete list of authors

  • Bengali, Ashfaq A||Fan, Wai Yip

publication date

  • October 2008