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