Regioselective formation of N-alkyl-3,5-pyrazole derived ligands. A synthetic and computational study

New N-alkyl-3,5-pyrazole derived ligands were synthesized by reaction between 3,5-pyrazole derived ligands and the appropriate haloalkane in toluene or THF using NaOEt or NaH as base. When the precursor ligand bears a pyridyl substituent the alkylation reaction presents a large regioselectivity. Theoretical calculations have been carried out to rationalize the experimental observations. It has been shown that regioselectivity is governed by the formation of Na+-pyrazolide chelate complexes.