The reactions of (2,6-difluorophenyl)phenylmethanone (2,6-F₂C₆H₃–C(O)–C₆H₅) (1) and (2,6-difluorophenyl)phenylmethanimine (2,6-F₂C₆H₃–C(NH)–C₆H₅) (3) with Fe(PMe₃)₄ afforded different selective C–F/C–H bond activation products. The reaction of 1 with Fe(PMe₃)₄ gave rise to bis-chelate iron(II) complex [C₆H₅–C(O)–3-FC₆H₃)Fe(PMe₃)]₂ (2) via C–F bond activation. The reaction of 3 with Fe(PMe₃)₄ delivered chelate hydrido iron(II) complex 2,6-F₂C₆H₃–C(NH)–C₆H₄)Fe(H)(PMe₃)₃ (4) through C–H bond activation. The DFT calculations show the detailed elementary steps of the mechanism of formation of hydrido complex 4 and indicate 4 is the kinetically preferred product. Complex 4 reacted with HCl, CH₃Br and CH₃I delivered the chelate iron halides (2,6-F₂C₆H₃–C(NH)–C₆H₄)Fe(PMe₃)₃X (X = Cl (5); Br (6); I (7)). A ligand (PMe₃) replacement by CO of 4 was observed giving (2,6-F₂C₆H₃–C(NH)–C₆H₄)Fe(H)(CO)(PMe₃)₂ (8). The chelate ligand exchange occurred through the reaction of 4 with salicylaldehydes. The reaction of 4 with Me₃SiCCH afforded (2,6-F₂C₆H₃–C(N)–C₆H₅)Fe(CC–SiMe₃)(PMe₃)₃ (11). A reaction mechanism from 4 to 11 was discussed with the support of IR monitoring. The molecular structures of complexes 2, 4, 6, 7, 10 and 11 were determined by X-ray diffraction.