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Isolation and reversible dimerization of a selenium–selenium three-electron σ-bond

Author

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  • Senwang Zhang

    (State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University)

  • Xingyong Wang

    (State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University)

  • Yuanting Su

    (State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University)

  • Yunfan Qiu

    (State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University)

  • Zaichao Zhang

    (Jiangsu Key Laboratory for the Chemistry of Low-dimensional Materials, School of Chemistry and Chemical Engineering, Huaiyin Normal University)

  • Xinping Wang

    (State Key Laboratory of Coordination Chemistry, School of Chemistry and Chemical Engineering, Nanjing University)

Abstract

Three-electron σ-bonding that was proposed by Linus Pauling in 1931 has been recognized as important in intermediates encountered in many areas. A number of three-electron bonding systems have been spectroscopically investigated in the gas phase, solution and solid matrix. However, X-ray diffraction studies have only been possible on simple noble gas dimer Xe∴Xe and cyclic framework-constrained N∴N radical cations. Here, we show that a diselena species modified with a naphthalene scaffold can undergo one-electron oxidation using a large and weakly coordinating anion, to afford a room-temperature-stable radical cation containing a Se∴Se three-electron σ-bond. When a small anion is used, a reversible dimerization with phase and marked colour changes is observed: radical cation in solution (blue) but diamagnetic dimer in the solid state (brown). These findings suggest that more examples of three-electron σ-bonds may be stabilized and isolated by using naphthalene scaffolds together with large and weakly coordinating anions.

Suggested Citation

  • Senwang Zhang & Xingyong Wang & Yuanting Su & Yunfan Qiu & Zaichao Zhang & Xinping Wang, 2014. "Isolation and reversible dimerization of a selenium–selenium three-electron σ-bond," Nature Communications, Nature, vol. 5(1), pages 1-7, September.
    • Handle: RePEc:nat:natcom:v:5:y:2014:i:1:d:10.1038_ncomms5127
    DOI: 10.1038/ncomms5127
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