Dewar–Chatt–Duncanson model
The Dewar–Chatt–Duncanson model is a model in organometallic chemistry that explains the chemical bonding in transition metal alkene complexes. The model is named after Michael J. S. Dewar,[1] Joseph Chatt and L. A. Duncanson.[2][3]
The alkene donates electron density into a π-acid metal d-orbital from a σ-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.
Similar to alkenes, alkynes adopt a similar bonding interaction, as shown in the image on the right. Not all alkyne-metal complexes utilize all four of these interactions for bonding (due to reasons like unviable d orbitals).Script error: No such module "Unsubst".
Main group elements can also form π-complexes with alkenes and alkynes. The β-diketiminato aluminum(I) complex Al{HC(CMeNAr)2} (Ar = 2,6-diisopropylphenyl), which bears an Al-based spx lone pair, reacts with alkenes and alkynes to give alumina(III)cyclopropanes and alumina(III)cyclopropenes in a process analogous to the formation of π-complexes by transition metals.[6][7] However, in most cases, the backbonding interaction is absent in these complexes due to the lack of energetically accessible filled orbitals for backdonation, resulting in π-complexes that dissociate readily and are therefore more challenging to observe or isolate.[8][9]
References
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- ↑ Dewar, M. Bulletin de la Société Chimique de France 1951, 1 8, C79
- ↑ "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 Script error: No such module "CS1 identifiers".
- ↑ 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 Script error: No such module "CS1 identifiers".
- ↑ Script error: No such module "citation/CS1"..
- ↑ Herrmann/Brauer: Synthetic Methods of Organometallic and Inorganic Chemistry Georg Thieme, Stuttgart, 1996
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