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

Journal Article


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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.

Authors


  •   Zhang, Senwang (external author)
  •   Wang, Xingyong
  •   Su, Yuanting (external author)
  •   Qiu, Yunfan (external author)
  •   Zhang, Zaichao (external author)
  •   Wang, Xinping (external author)

Publication Date


  • 2014

Geographic Focus


Citation


  • Zhang, S., Wang, X., Su, Y., Qiu, Y., Zhang, Z. & Wang, X. (2014). Isolation and reversible dimerization of a selenium–selenium three-electron σ-bond. Nature Communications, 5 (June), 4127.

Scopus Eid


  • 2-s2.0-84902323917

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4936&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3913

Start Page


  • 4127

Volume


  • 5

Issue


  • June

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.

Authors


  •   Zhang, Senwang (external author)
  •   Wang, Xingyong
  •   Su, Yuanting (external author)
  •   Qiu, Yunfan (external author)
  •   Zhang, Zaichao (external author)
  •   Wang, Xinping (external author)

Publication Date


  • 2014

Geographic Focus


Citation


  • Zhang, S., Wang, X., Su, Y., Qiu, Y., Zhang, Z. & Wang, X. (2014). Isolation and reversible dimerization of a selenium–selenium three-electron σ-bond. Nature Communications, 5 (June), 4127.

Scopus Eid


  • 2-s2.0-84902323917

Ro Full-text Url


  • http://ro.uow.edu.au/cgi/viewcontent.cgi?article=4936&context=smhpapers

Ro Metadata Url


  • http://ro.uow.edu.au/smhpapers/3913

Start Page


  • 4127

Volume


  • 5

Issue


  • June