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From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond

Author

Listed:
  • Chelladurai Ganesamoorthy

    (University of Duisburg-Essen)

  • Christoph Helling

    (University of Duisburg-Essen)

  • Christoph Wölper

    (University of Duisburg-Essen)

  • Walter Frank

    (Heinrich Heine University Düsseldorf)

  • Eckhard Bill

    (Max-Planck-Institute for Chemical Energy Conversion (CEC))

  • George E. Cutsail

    (Max-Planck-Institute for Chemical Energy Conversion (CEC))

  • Stephan Schulz

    (University of Duisburg-Essen)

Abstract

Neutral stibinyl and bismuthinyl radicals are typically short-lived, reactive species. Here we show the synthesis and solid-state structures of two stable stibinyl [L(Cl)Ga]2Sb· 1 and bismuthinyl radicals [L(I)Ga]2Bi· 4, which are stabilized by electropositive metal centers. Their description as predominantly metal-centered radicals is consistent with the results of NMR, EPR, SQUID, and DFT studies. The Lewis-acidic character of the Ga ligands allow for significant electron delocalization of the Sb- and Bi- unpaired radical onto the ligand. Single-electron reduction of [L(Cl)Ga]2Sb· gave LGaSbGa(Cl)L 5, the first compound containing a Ga=Sb double bond. The π-bonding contribution is estimated to 9.56 kcal mol−1 by NMR spectroscopy. The bonding situation and electronic structure is analyzed by quantum mechanical computations, revealing significant π backdonation from the Sb to the Ga atom. The formation of 5 illustrates the high-synthetic potential of 1 for the formation of new compounds with unusual electronic structures.

Suggested Citation

  • Chelladurai Ganesamoorthy & Christoph Helling & Christoph Wölper & Walter Frank & Eckhard Bill & George E. Cutsail & Stephan Schulz, 2018. "From stable Sb- and Bi-centered radicals to a compound with a Ga=Sb double bond," Nature Communications, Nature, vol. 9(1), pages 1-8, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-017-02581-2
    DOI: 10.1038/s41467-017-02581-2
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    Cited by:

    1. Xuyang Wang & Binglin Lei & Zhaoyin Zhang & Ming Chen & Hua Rong & Haibin Song & Lili Zhao & Zhenbo Mo, 2023. "Isolation and characterization of bis(silylene)-stabilized antimony(I) and bismuth(I) cations," Nature Communications, Nature, vol. 14(1), pages 1-11, December.

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