Cyclooctatetraenes Tetrakis-Annelated with α-Dithio- or α-Diselenocarbonyl Groups: Diradicals Predicted To Have Ground States with 10 π Electrons in the Eight-Membered Ring and Two-Center, Three-Electron, σ Bonds between Two Pairs of Chalcogen Atoms

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Article on cyclooctatetraenes tetrakis-annelated with α-dithio- or α-diselenocarbonyl groups.

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8 p.

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Zhou, Xin; Hrovat, David A. & Borden, Weston T. February 12, 2010.

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Article on cyclooctatetraenes tetrakis-annelated with α-dithio- or α-diselenocarbonyl groups.

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8 p.

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Reprinted with permission from the Journal of Physical Chemistry. Copyright 2010 American Chemical Society.

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Abstract: (U)B3LYP calculations with the 6-31+G(d) and 6-311+G(2df) basis sets have been carried out on cyclooctatetraenes 6 and 7, in which the COT ring is tetrakis-annelated with α-dithio- or α-diselenocarbonyl groups. Transferring two electrons from the high-lying b1g and eu σ MOs in 6 and 7 into the unoccupied, nonbonding, COT π orbital is computed to be energetically favorable. The lowest D4h electronic state is calculated to be 3Eu, which formally contains 10 π electrons in the eight-membered ring and has two unpaired electrons in σ MOs. The 3Eu state undergoes a first-order Jahn-Teller distortion to form 6d and 7d, in which the pair of one-electron holes in the σ MOs is stabilized by the formation of two, two-center, three-electron bonds between pairs of chalcogen atoms that are diagonally across the eight-membered ring from each other. The corresponding open-shell singlets are computed to be about 1 kcal/mol lower in energy than the Jahn-Teller distorted triplets. Molecules 6i and 7i, in which the C-C bond in one four-membered ring is cleaved, are computed to be lower in energy than 6d and 7d. However, a substantial barrier is predicted to separate each of the two pairs of isomers so that 6d and 7d should, at least in principle, be isolable.

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  • Journal of Physical Chemistry A, 2010, Washington D.C.: American Chemical Society, pp. 3683-3690

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  • Publication Title: Journal of Physical Chemistry A
  • Volume: 114
  • Page Start: 3683
  • Page End: 3690
  • Peer Reviewed: Yes

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  • February 12, 2010

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  • Jan. 31, 2012, 10:30 a.m.

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  • Aug. 30, 2017, 3:08 p.m.

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Zhou, Xin; Hrovat, David A. & Borden, Weston T. Cyclooctatetraenes Tetrakis-Annelated with α-Dithio- or α-Diselenocarbonyl Groups: Diradicals Predicted To Have Ground States with 10 π Electrons in the Eight-Membered Ring and Two-Center, Three-Electron, σ Bonds between Two Pairs of Chalcogen Atoms, article, February 12, 2010; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc71813/: accessed October 17, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.