Reactivity of the M-(η2-alkyne) bond [M = Cr, W]

A kinetic and DFT study

Bert H G Swennenhuis, G. Benjamin Cieslinski, Edward Brothers, Ashfaq A. Bengali

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

The displacement of η2-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)52-1-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-(η2-alkyne) bond strength.

Original languageEnglish
Pages (from-to)891-897
Number of pages7
JournalJournal of Organometallic Chemistry
Volume695
Issue number6
DOIs
Publication statusPublished - 15 Mar 2010

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Alkynes
alkynes
Carbon Monoxide
Discrete Fourier transforms
reactivity
Kinetics
Metals
kinetics
metals
Enthalpy
Ligands
Information Systems
enthalpy
fragments
dissociation
ligands
energy

Keywords

  • Flash photolysis
  • Kinetics
  • Photochemistry

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Inorganic Chemistry
  • Materials Chemistry

Cite this

Reactivity of the M-(η2-alkyne) bond [M = Cr, W] : A kinetic and DFT study. / Swennenhuis, Bert H G; Benjamin Cieslinski, G.; Brothers, Edward; Bengali, Ashfaq A.

In: Journal of Organometallic Chemistry, Vol. 695, No. 6, 15.03.2010, p. 891-897.

Research output: Contribution to journalArticle

Swennenhuis, Bert H G ; Benjamin Cieslinski, G. ; Brothers, Edward ; Bengali, Ashfaq A. / Reactivity of the M-(η2-alkyne) bond [M = Cr, W] : A kinetic and DFT study. In: Journal of Organometallic Chemistry. 2010 ; Vol. 695, No. 6. pp. 891-897.
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