Dewar–Chatt–Duncanson model

The Dewar–Chatt–Duncanson model is a model in organometallic chemistry that explains the type of chemical bonding between an alkene and a metal (π-complex) in certain organometallic compounds. The model is named after Michael J. S. Dewar,[1] Joseph Chatt and L. A. Duncanson.[2][3]

Orbital interactions in a metal-ethylene complex. On the left, a filled pi-orbital on C2H4 overlaps with an empty d-orbital on the metal. On the right, an empty pi-antibonding orbital on C2H4 overlaps with a filled d-orbital on the metal

The π-acid alkene donates electron density into a metal d-orbital from a π-symmetry bonding orbital between the carbon atoms. The metal donates electrons back from a (different) filled d-orbital into the empty π* antibonding orbital. Both of these effects tend to reduce the carbon-carbon bond order, leading to an elongated C−C distance and a lowering of its vibrational frequency.

In Zeise's salt K[PtCl3(C2H4)].H2O the C−C bond length has increased to 134 picometres from 133 pm for ethylene. In the nickel compound Ni(C2H4)(PPh3)2 the value is 143 pm.

The interaction also causes carbon atoms to "rehybridise" from sp2 towards sp3, which is indicated by the bending of the hydrogen atoms on the ethylene back away from the metal.[4] In silico calculations show that 75% of the binding energy is derived from the forward donation and 25% from backdonation.[5] This model is a specific manifestation of the more general π backbonding model.

References
  1. Dewar, M. Bulletin de la Société Chimique de France 1951, 1 8, C79
  2. "Olefin co-ordination compounds. Part III. Infra-red spectra and structure: attempted preparation of acetylene complexes" J. Chatt and L. A. Duncanson, Journal of the Chemical Society, 1953, 2939 doi:10.1039/JR9530002939
  3. Directing effects in inorganic substitution reactions. Part I. A hypothesis to explain the trans-effect J. Chatt, L. A. Duncanson, L. M. Venanzi, Journal of the Chemical Society, 1955, 4456-4460 doi:10.1039/JR9550004456
  4. Miessler, Gary L.; Donald A. Tarr (2004). Inorganic Chemistry. Upper Saddle River, New Jersey: Pearson Education, Inc. Pearson Prentice Hall. ISBN 0-13-035471-6..
  5. Herrmann/Brauer: Synthetic Methods of Organometallic and Inorganic Chemistry Georg Thieme, Stuttgart, 1996
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