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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.; Gastel, Maurice van; Hinz, Alexander; Ghadwal, Rajendra S.

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‐iPr$_{2}$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$_{4}$)$_{2}$.

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Verlagsausgabe §
DOI: 10.5445/IR/1000130815
Veröffentlicht am 25.03.2021
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Anorganische Chemie (AOC)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2021
Sprache Englisch
Identifikator ISSN: 0947-6539, 1521-3765
KITopen-ID: 1000130815
Erschienen in Chemistry - A European Journal
Verlag Wiley
Band 27
Seiten 1-8
Schlagwörter arsenic; coordination modes; iron; phosphorus; radical ions
Nachgewiesen in Scopus
Web of Science
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