Metalloradical Cations and Dications Based on Divinyldiphosphene and 
Divinyldiarsene Ligands

Sharma, Mahendra K.; Rottschäfer, Dennis; Neumann, Beate; Stammler, Hans-Georg; Danés, Sergi; Andrada, Diego M.; van Gastel, Maurice; Hinz, Alexander; Ghadwal, Rajendra S.

doi:10.1002/chem.202100213

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Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands

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van Gastel, Maurice
Research Group van Gastel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Sharma, M. K., Rottschäfer, D., Neumann, B., Stammler, H.-G., Danés, S., Andrada, D. M., et al. (2021). Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands. Chemistry – A European Journal, 27(18), 5803-5809. doi:10.1002/chem.202100213.

Cite as: https://hdl.handle.net/21.11116/0000-0008-479C-9

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‐EEC_vinyl) 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‐EEC_vinyl to η³‐EC_vinylC_Ph coordination shuttling to form the dications (4‐E)(GaCl₄)₂.