Dewar-Chatt-Duncanson model
- Dewar-Chatt-Duncanson model
The Dewar-Chatt-Duncanson model is a model in organometallic chemistry which explains the type of chemical bonding between an alkene and a metal (pi-complex) in certain organometallic compounds. The model is named after Michael J. S. Dewar [Dewar, M. Bull. Soc. Chim. Fr. 1951, 1 8 , C79] , Joseph Chatt and L. A. Duncanson ["Olefin co-ordination compounds. Part III. Infra-red spectra and structure: attempted preparation of acetylene complexes" J. Chatt and L. A. Duncanson, J. Chem. Soc., 1953, 2939 DOI|10.1039/JR9530002939] ["Directing effects in inorganic substitution reactions. Part I. A hypothesis to explain the trans-effect" J. Chatt, L. A. Duncanson, L. M. Venanzi, J. Chem. Soc., 1955, 4456-4460 DOI|10.1039/JR9550004456 ] .
The pi-acid alkene donates electron density into a metal d-orbital from π-symmetry bonding orbital between the carbon atoms (I). The metal donates electrons back from (a different) filled d-orbital into the empty π* antibonding orbital (II). Both of these effects tend to reduce the carbon-carbon bond order, leading to an elongated C-C distance and a lowering its vibrational frequency.
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In Zeise's salt K [PtCl3(C2H4)] .H2O the C-C bond length has increased to 134 picometer from 133 pm for ethylene. In the nickel compound Ni(CH2CH2)(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. [cite book|last=Miessler|first=Gary L.|coauthors=Donald A. Tarr|year=2004|title=Inorganic Chemistry|publisher=Pearson Education, Inc. Pearson Prentice Hall|location=Upper Saddle River, New Jersey|id=ISBN 0-13-035471-6.] In silico calculations show that 75% of the binding energy is derived from the forward donation and 25% from backdonation [Herrmann/Brauer: "Synthetic Methods of Organometallic and Inorganic Chemistry" Georg Thieme, Stuttgart, 1996] . This model is a specific manifestation of the more general pi backbonding model.
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Dewar–Chatt–Duncanson model — The Dewar–Chatt–Duncanson model is a model in organometallic chemistry which explains the type of chemical bonding between an alkene and a metal (pi complex) in certain organometallic compounds. The model is named after Michael J. S. Dewar,[1]… … Wikipedia
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