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Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands.

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}2 Fe(CO)3 ].+ , E = P or As; IPr = C{(NDipp)CH}2 , Dipp = 2,6-iPr2 C6 H3 ] 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}2 Fe(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 -ECvinyl CPh coordination shuttling to form the dications (4-E)(GaCl4 )2 .

SUBMITTER: Sharma MK 

PROVIDER: S-EPMC8048781 | biostudies-literature | 2021 Mar

REPOSITORIES: biostudies-literature

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Metalloradical Cations and Dications Based on Divinyldiphosphene and Divinyldiarsene Ligands.

Sharma Mahendra K MK   Rottschäfer Dennis D   Neumann Beate B   Stammler Hans-Georg HG   Danés Sergi S   Andrada Diego M DM   van Gastel Maurice M   Hinz Alexander A   Ghadwal Rajendra S RS  

Chemistry (Weinheim an der Bergstrasse, Germany) 20210303 18

Metalloradicals are key species in synthesis, catalysis, and bioinorganic chemistry. Herein, two iron radical cation complexes (3-E)GaCl<sub>4</sub> [(3-E)<sup>.+</sup> = [{(IPr)C(Ph)E}<sub>2</sub> Fe(CO)<sub>3</sub> ]<sup>.+</sup> , E = P or As; IPr = C{(NDipp)CH}<sub>2</sub> , Dipp = 2,6-iPr<sub>2</sub> C<sub>6</sub> H<sub>3</sub> ] are reported as crystalline solids. Treatment of the divinyldipnictenes {(IPr)C(Ph)E}<sub>2</sub> (1-E) with Fe<sub>2</sub> (CO)<sub>9</sub> affords [{(IPr)C(Ph)E}  ...[more]

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