Carbon-hydrogen activation of cycloalkanes by cyclopentadienylcarbonylrhodium--a lifetime enigma. Academic Article uri icon

abstract

  • Carbon-hydrogen bond activation reactions of four cycloalkanes (C5H10, C6H12, C7H14, and C8H16) by the Cp'Rh(CO) fragments (Cp' = η(5)-C5H5 (Cp) or η(5)-C5Me5 (Cp*)) were modeled theoretically by combining density functional and coupled cluster theories, and their reaction rates were measured by fast time-resolved infrared spectroscopy. The reaction has two steps, starting with the formation of a σ-complex intermediate, followed by oxidative addition of the C-H bond by the rhodium. A range of σ-complex stabilities among the electronically unique C-H bonds in a cycloalkane were calculated and are related to the individual strengths of the C-H bond's interactions with the Rh fragment and the steric repulsion that is incurred upon forming the specific σ-complex. The unexpectedly large increase in the lifetimes of the σ-complexes from cyclohexane to cycloheptane was predicted to be due to the large range of stabilities of the different σ-complexes found for cycloheptane. The reaction lifetimes were simulated with two mechanisms, with and without migrations among the different σ-complexes, to determine if ring migrations prior to C-H activation were influencing the rate. Both mechanisms predicted similar lifetimes for cyclopentane, cyclohexane, and, to a lesser extent, cycloheptane, suggesting ring migrations do not have a large impact on the rate of C-H activation for these cycloalkanes. For cyclooctane, the inclusion of ring migrations in the reaction mechanism led to a more accurate prediction of the lifetime, indicating that ring migrations did have an effect on the rate of C-H activation for this alkane, and that migration among the σ-complexes is faster than the C-H activation for this larger cycloalkane.

published proceedings

  • J Am Chem Soc

author list (cited authors)

  • Pitts, A. L., Wriglesworth, A., Sun, X., Calladine, J. A., Zarić, S. D., George, M. W., & Hall, M. B

citation count

  • 27

complete list of authors

  • Pitts, Amanda L||Wriglesworth, Alisdair||Sun, Xue-Zhong||Calladine, James A||Zarić, Snežana D||George, Michael W||Hall, Michael B

publication date

  • June 2014