Time-Resolved Infrared Spectroscopy Studies of Olefin Binding in Photogeneratecl CpRu(CO)X (X = Cl, I) Transients Academic Article uri icon

abstract

  • The mechanism and energetics of ligand (L) substitution (L = THF, cyclopentene, cyclohexene, cyclooctene) from photogenerated CpRu(CO)(X)L (X = Cl, I) complexes were studied using time-resolved infrared spectroscopy. The reactions proceed through a dissociative mechanism, and the Ru-L binding enthalpies were estimated. The trend in the bond enthalpies, Ru-( 2-cyclooctene) Ru-( 2-cyclopentene) > Ru-( 2-cyclohexene), is correlated with the strain energy of the cycloalkene ring. For all ligands investigated, CpRu(CO)(Cl)-L binding enthalpies were lower than those for the analogous CpMn(CO) 2-L and BzCr(CO) 2-L complexes. DFT calculations indicate that the lower binding enthalpy for the Ru-L complexes is due to a greater reorganizational energy for the CpRu(CO)Cl fragment as it adopts a configuration suitable for interaction with the ligand. 2012 American Chemical Society.

published proceedings

  • ORGANOMETALLICS

altmetric score

  • 1

author list (cited authors)

  • Muhammad, S., Kyran, S. J., Raju, R. K., Brothers, E. N., Darensbourg, D. J., & Bengali, A. A.

citation count

  • 3

complete list of authors

  • Muhammad, Sohail||Kyran, Samuel J||Raju, Rajesh K||Brothers, Edward N||Darensbourg, Donald J||Bengali, Ashfaq A

publication date

  • January 2012