Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands

Metalloradicals are key species in synthesis, catalysis, and bioinorganic chemistry. Herein, two iron radical cation complexes (3‐E)GaCl$_{4}$ [(3‐E)$^{.+}$ = [{(IPr)C(Ph)E}$_{2}$Fe(CO)$_{3}$]$^{.+}$, E = P or As; IPr = C{(NDipp)CH}$_{2}$, Dipp = 2,6‐iPr$_{2}$C$_{6}$H$_{3}$] are reported as crystalline solids. Treatment of the divinyldipnictenes {(IPr)C(Ph)E}$_{2}$ (1‐E) with 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 (η$^{3}$‐EEC$_{vinyl}$) fashion and functions as a 4e donor ligand. Complexes 2‐E undergo 1e oxidation with GaCl$_{3}$ to yield (3‐E)GaCl$_{4}$. Spin density analysis revealed that the unpaired electron in (3‐E).+ is mainly located on the Fe (52–64 %) and vinylic C (30–36 %) atoms. Further 1e oxidation of (3‐E)GaCl$_{4}$ leads to unprecedented η$^{3}$‐EEC$_{vinyl}$ to η$^{3}$‐EC$_{vinyl}$C$_{Ph}$ coordination shuttling to form the dications (4‐E)(GaCl$_{4}$)$_{2}$.