Single-Electron Oxidation of Carbene-Coordinated Pnictinidenes-Entry into Heteroleptic Radical Cations and Metalloid Clusters

Julia Krüger; Julia Haak; Christoph Wölper; George E Cutsail 3rd; Gebhard Haberhauer; Stephan Schulz

doi:10.1021/acs.inorgchem.2c00249

Single-Electron Oxidation of Carbene-Coordinated Pnictinidenes-Entry into Heteroleptic Radical Cations and Metalloid Clusters

Inorg Chem. 2022 Apr 18;61(15):5878-5884. doi: 10.1021/acs.inorgchem.2c00249. Epub 2022 Mar 25.

Authors

Julia Krüger¹, Julia Haak², Christoph Wölper¹, George E Cutsail 3rd^{1

2}, Gebhard Haberhauer³, Stephan Schulz^{1

4}

Affiliations

¹ Institute of Inorganic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, 45141 Essen, Germany.
² Max Planck Institute for Chemical Energy Conversion (CEC), Stiftstraße 34-36, 45470 Mülheim an der Ruhr, Germany.
³ Institute of Organic Chemistry, University of Duisburg-Essen, Universitätsstraße 5-7, 45141 Essen, Germany.
⁴ Center for Nanointegration Duisburg-Essen (CENIDE), University of Duisburg-Essen, Carl-Benz-Straße 199, 47057 Duisburg, Germany.

PMID: 35333051
DOI: 10.1021/acs.inorgchem.2c00249

Abstract

Stable heavy main group element radicals are challenging synthetic targets. Although several strategies have been developed to stabilize such odd-electron species, the number of heavier pnictogen-centered radicals is limited. We report on a series of two-coordinated pnictogen-centered radical cations [(^MecAAC)EGa(Cl)L][B(C₆F₅)₄] (^MecAAC = [H₂C(CMe₂)₂NDipp]C; Dipp = 2,6-i-Pr₂C₆H₃; E = As 1, Sb 2, Bi 3; L = HC[C(Me)NDipp]₂) synthesized by one-electron oxidation of L(Cl)Ga-substituted pnictinidenes (^MecAAC)EGa(Cl)L (E = As I, Sb II, Bi III). 1-3 were characterized by electron paramagnetic resonance (EPR) spectroscopy and single crystal X-ray diffraction (sc-XRD) (1, 2), while quantum chemical calculations support their description as carbene-coordinated pnictogen-centered radical cations. The low thermal stability of 3 enables access to metalloid bismuth clusters as shown by formation of [{LGa(Cl)}₃Bi₆][B(C₆F₅)₄] (4).