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Time-Resolved Infrared Spectroscopy Studies of Olefin Binding in Photogenerated CpRu(CO)X (X = Cl, I) Transients
Sohail Muhammad, Samuel J. Kyran, Rajesh K. Raju?, Edward N. Brothers, Donald J. Darensbourg, and Ashfaq A. BengaliDepartment of Chemistry, Texas A&M University at Qatar, Doha, Qatar
Department of Chemistry, Texas A&M University, College Station, Texas 77843, United States
Organometallics, 2012, 31 (10), pp 3972-3979
DOI: 10.1021/om300197b
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-(n2-cyclooctene) = Ru-(n2-cyclopentene) > Ru-(n2-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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