Time-resolved infrared spectroscopy studies of olefin binding in photogenerated CpRu(CO)X (X = Cl, I) transients

Muhammad Sohail, Samuel J. Kyran, Rajesh K. Raju, Edward 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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Alkenes
Carbon Monoxide
alkenes
Infrared spectroscopy
enthalpy
infrared spectroscopy
Enthalpy
Cyclopentanes
ligands
Ligands
Cycloparaffins
Strain energy
Discrete Fourier transforms
fragments
substitutes
trends
Substitution reactions
energy
rings
configurations

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Time-resolved infrared spectroscopy studies of olefin binding in photogenerated CpRu(CO)X (X = Cl, I) transients. / Sohail, Muhammad; Kyran, Samuel J.; Raju, Rajesh K.; Brothers, Edward; Darensbourg, Donald J.; Bengali, Ashfaq A.

In: Organometallics, Vol. 31, No. 10, 28.05.2012, p. 3972-3979.

Research output: Contribution to journalArticle

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AU - Kyran, Samuel J.

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AU - Brothers, Edward

AU - Darensbourg, Donald J.

AU - Bengali, Ashfaq A.

PY - 2012/5/28

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N2 - 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.

AB - 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.

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