Reactivity of the M-(eta(2)-alkyne) bond [M = Cr, W]: A kinetic and DFT study Academic Article uri icon


  • The displacement of 2-coordinated 1-hexyne and 3-hexyne by 2-picoline from the Cr(CO)5, BzCr(CO)2 and W(CO)5 fragments was studied. For the Cr systems, the data is consistent with a dissociative mechanism of alkyne displacement from the metal center. For W(CO)5(2-1-hexyne), the alkyne displacement follows a largely associative mechanism. The bond dissociation enthalpies obtained from the kinetic analysis are in good agreement with the values obtained by detailed DFT calculations. The calculations indicate that the energy required for the steric reorganization of the alkyne ligand prior to binding with the metal is an important factor in the determination of the overall metal-(2-alkyne) bond strength. 2010 Elsevier B.V. All rights reserved.

published proceedings


author list (cited authors)

  • Swennenhuis, B., Cieslinski, G. B., Brothers, E. N., & Bengali, A. A.

citation count

  • 10

complete list of authors

  • Swennenhuis, Bert HG||Cieslinski, G Benjamin||Brothers, Edward N||Bengali, Ashfaq A

publication date

  • January 2010