Solvation and structural effects on the stability of 10-X-2 ate-complexes: a computational study.

The structures and energies of a variety of 10-X-2 ate-complexes derived from reaction of alkyllithiums and aryllithiums with the corresponding organohalides have been studied at the B3LYP/6-31+2G** theoretical level. The results of the calculations, which are in good agreement with the available experimental data, indicate that diaryl ate-complexes are more stable than their dialkyl counterparts. Fluorine substitution was found to confer substantial stability to both diaryl and dialkyl ate-complexes, and the calculations suggest that perfluoro dialkyl 10-X-2 ate-complexes should be experimentally observable species. One of the most important factors contributing to stability of a 10-X-2 ate-complex is removal of the formally cationic lithium from the vicinity of the ate-anion via coordination with a Lewis basic solvent.