Displacement kinetics of η2-bound furan and 2,3-dihydrofuran from Mn and Cr centers

Evidence for the partial dearomatization of the furan ligand

Jeremy R. Andreatta, G. Benjamin Cieslinski, Madeeha Batool, Xue Zhong Sun, Michael W. George, Edward Brothers, Donald J. Darensbourg, Ashfaq A. Bengali

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The displacement of η2-coordinated ligands from the photolytically generated CpMn(CO)2L and BzCr(CO)2L [Cp = η5-C5H5, Bz = η6-C 6H6, L = 2,3-dihydrofuran (DHF), furan] complexes by pyridine has been studied. The displacement reactions span a wide range of time scales from microseconds to hours and were studied using a range of time-resolved IR spectroscopic techniques. The substitution reactions follow a dissociative pathway and the measured activation enthalpies provide an estimate for the strength of the metal - (η2-furan) and metal - (η2-DHF) interactions. In these complexes, the Cr center binds both ligands weaker than the Mn center. There is a ∼6-10 kcal/mol difference in the binding enthalpies of η2-furan and η2-DHF to both metals suggesting that this difference is the result of a partial loss of resonance energy in the case of the aromatic furan ligand upon interaction with the metal.

Original languageEnglish
Pages (from-to)7787-7793
Number of pages7
JournalInorganic Chemistry
Volume48
Issue number16
DOIs
Publication statusPublished - 17 Aug 2009

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furans
Metals
Ligands
ligands
Kinetics
kinetics
Carbon Monoxide
metals
Enthalpy
enthalpy
pyridines
Substitution reactions
Chemical activation
interactions
activation
substitutes
2,3-dihydrofuran
furan
estimates
energy

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Displacement kinetics of η2-bound furan and 2,3-dihydrofuran from Mn and Cr centers : Evidence for the partial dearomatization of the furan ligand. / Andreatta, Jeremy R.; Cieslinski, G. Benjamin; Batool, Madeeha; Sun, Xue Zhong; George, Michael W.; Brothers, Edward; Darensbourg, Donald J.; Bengali, Ashfaq A.

In: Inorganic Chemistry, Vol. 48, No. 16, 17.08.2009, p. 7787-7793.

Research output: Contribution to journalArticle

Andreatta, Jeremy R. ; Cieslinski, G. Benjamin ; Batool, Madeeha ; Sun, Xue Zhong ; George, Michael W. ; Brothers, Edward ; Darensbourg, Donald J. ; Bengali, Ashfaq A. / Displacement kinetics of η2-bound furan and 2,3-dihydrofuran from Mn and Cr centers : Evidence for the partial dearomatization of the furan ligand. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 16. pp. 7787-7793.
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abstract = "The displacement of η2-coordinated ligands from the photolytically generated CpMn(CO)2L and BzCr(CO)2L [Cp = η5-C5H5, Bz = η6-C 6H6, L = 2,3-dihydrofuran (DHF), furan] complexes by pyridine has been studied. The displacement reactions span a wide range of time scales from microseconds to hours and were studied using a range of time-resolved IR spectroscopic techniques. The substitution reactions follow a dissociative pathway and the measured activation enthalpies provide an estimate for the strength of the metal - (η2-furan) and metal - (η2-DHF) interactions. In these complexes, the Cr center binds both ligands weaker than the Mn center. There is a ∼6-10 kcal/mol difference in the binding enthalpies of η2-furan and η2-DHF to both metals suggesting that this difference is the result of a partial loss of resonance energy in the case of the aromatic furan ligand upon interaction with the metal.",
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AU - George, Michael W.

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AU - Darensbourg, Donald J.

AU - Bengali, Ashfaq A.

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