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Concept
Complexe de transfert de charge
Résumé
In chemistry, a charge-transfer (CT) complex or electron-donor-acceptor complex describes a type of supramolecular assembly of two or more molecules or ions. The assembly consists of two molecules that self-attract through electrostatic forces, i.e., one has at least partial negative charge and the partner has partial positive charge, referred to respectively as the electron acceptor and electron donor. In some cases, the degree of charge transfer is "complete", such that the CT complex can be classified as a salt. In other cases, the charge-transfer association is weak, and the interaction can be disrupted easily by polar solvents.
A number of organic compounds form charge-transfer complex, which are often described as electron-donor-acceptor complexes (EDA complexes). Typical acceptors are nitrobenzenes or tetracyanoethylene. The strength of their interaction with electron donors correlates with the ionization potentials of the components. For TCNE, the stability constants (L/mol) for its complexes with benzene derivatives correlates with the number of methyl groups: benzene (0.128), 1,3,5-trimethylbenzene (1.11), 1,2,4,5-tetramethylbenzene (3.4), and hexamethylbenzene (16.8).
1,3,5-Trinitrobenzene and related polynitrated aromatic compounds, being electron-deficient, form charge-transfer complexes with many arenes. Such complexes form upon crystallization, but often dissociate in solution to the components. Characteristically, these CT salts crystallize in stacks of alternating donor and acceptor (nitro aromatic) molecules, i.e. A-B-A-B.
Dihalogens X2 (X = Cl, Br, I) and interhalogens XY(X = I; Y = Cl, Br) are Lewis acid species capable of forming a variety of products when reacted with donor species. Among these species (including oxidation or protonated products), CT adducts D·XY have been largely investigated. The CT interaction has been quantified and is the basis of many schemes for parameterizing donor and acceptor properties, such as those devised by Gutmann, Childs, Beckett, and the ECW model.
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