Metalloradicals are key species in synthesis, catalysis, andb ioinorganic chemistry.H erein, two iron radical cation complexes (3-E)GaCl 4 [(3-E)C + = [{(IPr)-C(Ph)E} 2 Fe(CO) 3 ]C + ,E= Po rA s; IPr = C{(NDipp)CH} 2 ,D ipp = 2,6-iPr 2 C 6 H 3 ]a re reported as crystallines olids. Treatment of the divinyldipnictenes {(IPr)C(Ph)E} 2 (1-E)w ith Fe 2 (CO) 9 affords [{(IPr)C(Ph)E} 2 Fe(CO) 3 ](2-E), in which 1-E binds to the Fe atom in an allylic (h 3-EEC vinyl)f ashion and functions as a 4e donor ligand.C omplexes 2-E undergo 1e oxidation with GaCl 3 to yield (3-E)GaCl 4 .S pin density analysisr evealed that the unpaired electron in (3-E)C + is mainly located on the Fe (52-64%)a nd vinylic C(30-36 %) atoms. Further 1e oxidation of (3-E)GaCl 4 leads to unprecedented h 3-EEC vinyl to h 3-EC vinyl C Ph coordinations huttling to form the dications (4-E)(GaCl 4) 2 .