Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands
Mahendra K. Sharma, Dennis Rottschäfer, Beate Neumann, Hans‐Georg Stammler, Sergi Danés, Diego M. Andrada, Maurice van Gastel, Alexander Hinz, Rajendra S. Ghadwal
Abstract
Abstract 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‐ i Pr 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 .