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Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands
Author(s) -
Sharma Mahendra K.,
Rottschäfer Dennis,
Neumann Beate,
Stammler HansGeorg,
Danés Sergi,
Andrada Diego M.,
Gastel Maurice,
Hinz Alexander,
Ghadwal Rajendra S.
Publication year - 2021
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202100213
Subject(s) - chemistry , allylic rearrangement , ligand (biochemistry) , catalysis , medicinal chemistry , unpaired electron , bioinorganic chemistry , yield (engineering) , stereochemistry , crystallography , inorganic chemistry , molecule , organic chemistry , materials science , biochemistry , receptor , metallurgy
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 .