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Free keywords:
arsenic; coordination modes; iron; phosphorus; radical ions
Abstract:
Metalloradicals are key species in synthesis, catalysis, and bioinorganic chemistry. Herein, two iron radical cation complexes (3‐E)GaCl4 [(3‐E).+ = [{(IPr)C(Ph)E}2Fe(CO)3].+, E = P or As; IPr = C{(NDipp)CH}2, Dipp = 2,6‐iPr2C6H3] are reported as crystalline solids. Treatment of the divinyldipnictenes {(IPr)C(Ph)E}2 (1‐E) with Fe2(CO)9 affords [{(IPr)C(Ph)E}2Fe(CO)3] (2‐E), in which 1‐E binds to the Fe atom in an allylic (η3‐EECvinyl) fashion and functions as a 4e donor ligand. Complexes 2‐E undergo 1e oxidation with GaCl3 to yield (3‐E)GaCl4. 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)GaCl4 leads to unprecedented η3‐EECvinyl to η3‐ECvinylCPh coordination shuttling to form the dications (4‐E)(GaCl4)2.
