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–(η2-cyclooctene) ≈ Ru–(η2-cyclopentene) > Ru–(η2-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.
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