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, Ashfaq A. Bengali

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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-(η 2-cyclooctene) ≈ Ru-(η 2-cyclopentene) > Ru-(η 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.

Original languageEnglish
Pages (from-to)3972-3979
Number of pages8
JournalOrganometallics
Volume31
Issue number10
DOIs
Publication statusPublished - 28 May 2012

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ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry

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