A novel fluorinated ligand, the anionic PhB(CH2P(p-CF3C6H4)2)3 (PhBP3 (p-CF3Ph)), has been synthesized and characterized, as well as its corresponding thallium, copper, and silver derivatives. The presence of fluorine atoms in the ligand structure induced the desired effect of enhancing electrophilic character at the metal center, without promoting substantial changes in the ligand skeleton compared with the parent ligand PhB(CH2PPh2)3(-) (PhBP3). Olefin aziridination and C-H amidation reactions have been induced with those complexes as catalyst precursors. The copper derivative catalyzed the olefin aziridination of an array of olefins bearing either electron-donating or electron-withdrawing groups. The silver analogue was found to promote the C-H amidation of a series of substrates in moderate to high yields.