Displacement kinetics of eta(2)-bound furan and 2,3-dihydrofuran from Mn and Cr centers: evidence for the partial dearomatization of the furan ligand.
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abstract
The displacement of eta(2)-coordinated ligands from the photolytically generated CpMn(CO)(2)L and BzCr(CO)(2)L [Cp = eta(5)-C(5)H(5), Bz = eta(6)-C(6)H(6), 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-(eta(2)-furan) and metal-(eta(2)-DHF) interactions. In these complexes, the Cr center binds both ligands weaker than the Mn center. There is a approximately 6-10 kcal/mol difference in the binding enthalpies of eta(2)-furan and eta(2)-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.
Andreatta, J. R., Cieslinski, G. B., Batool, M., Sun, X., George, M. W., Brothers, E. N., Darensbourg, D. J., & Bengali, A. A.
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Andreatta, Jeremy R||Cieslinski, G Benjamin||Batool, Madeeha||Sun, Xue-Zhong||George, Michael W||Brothers, Edward N||Darensbourg, Donald J||Bengali, Ashfaq A
