Preparation of carboxylic arylphosphines by hydrolysis of the trifluoromethyl group

Triarylphosphines substituted with carboxylic and trifluoromethlyl groups have been prepared by the hydrolysis of trifluoromethyl groups using fuming sulfuric acid and boric acid. The reaction has been studied in a set of homoleptic and heteroleptic trifluoromethylated triarylphosphines and offers a new synthetic procedure for the preparation of carboxylic phosphines with a relatively simple methodology. The degree of carboxylation is modulated by the reaction conditions and is sensitive to the substitution pattern of the starting trifluoromethylated phosphines. A pH-dependent procedure based on the amphiphilic character of these phosphines was developed for their separation and purification. The electronic properties of the synthesized carboxylic-trifluoromethylated phosphines have been analyzed by (31)P NMR of the corresponding selenide derivatives. Finally, the structures of two palladium complexes, containing the para and meta carboxylic-trifluoromethylated phosphines are also described, showing different dimeric structures.