Abstract
Labile charge-transfer complexes (CTC) are examined for C6H5X with electron-donor organic compounds D that contain heteroatoms with nonbonding pairs (O, N, and Cl). The n(V) isotherms (derived by refractometry, and sometimes supplemented by other methods) for over 400 liquid C6H5X-D systems are surveyed to show that C6H5X shows the greatest tendency to form complexes if X is a type II (m-orienting) substituent, the tendency also increasing with the dipole moment of the molecule and decreasing as O≥Cl>N for the heteroatoms in D, though not in proportion to the basicity of the nonbenzenoid component. The C6H5X-D compounds are of donor-acceptor type and are due to electron transfer from D to an aromatic ring with reduced π-electron density. These complexes differ from ordinary aromatic π-complexes in having reverse displacement of the π-electrons; they might be called reverse π-complexes. It is proposed that these reverse π-complexes are formed as initial intermediates in nucleophilic aromatic substitution.
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The results are largely illustrative; detailed refractometric data for over 400 systems have been given elsewhere [20]. The other physicochemical studies will appear in future papers.
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Voronkov, M.G., Deich, A.Y. Formation of charge-transfer complexes between monosubstituted benzenes C6H5X and electron-donor organic compounds. Theor Exp Chem 1, 443–449 (1967). https://doi.org/10.1007/BF00525388
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DOI: https://doi.org/10.1007/BF00525388