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Through-bond orbital coupling in end-functionalized bicyclohexylidenes: photoelectron spectroscopy and ab initio SCF-MO calculations

To establish whether through-bond (TB) orbital interactions occur between the functional groups and the hydrocarbon skeleton in a series of end-functionalized oligo(cyclohexylidenes) 1−12, their HeI photoelectron (PE) spectra were measured and analyzed. Vertical ionization energies, Ivj, of the high...

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Hauptverfasser: Marsman, Albert W. (VerfasserIn) , Havenith, Remco W. A. (VerfasserIn) , Bethke, Sabine (VerfasserIn) , Jenneskens, Leonardus W. (VerfasserIn) , Gleiter, Rolf (VerfasserIn) , Lenthe, Joop H. van (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 07 September 2000
In: European journal of organic chemistry
Year: 2000, Heft: 14, Pages: 2629-2641
ISSN:1099-0690
DOI:10.1002/1099-0690(200007)2000:14<2629::AID-EJOC2629>3.0.CO;2-6
Online-Zugang:Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1002/1099-0690(200007)2000:14<2629::AID-EJOC2629>3.0.CO;2-6
Verlag, lizenzpflichtig, Volltext: https://chemistry-europe.onlinelibrary.wiley.com/doi/abs/10.1002/1099-0690%28200007%292000%3A14%3C2629%3A%3AAID-EJOC2629%3E3.0.CO%3B2-6
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Verfasserangaben:Albert W. Marsman, Remco W. A. Havenith, Sabine Bethke, Leonardus W. Jenneskens, Rolf Gleiter, and Joop H. van Lenthe
Beschreibung
Zusammenfassung:To establish whether through-bond (TB) orbital interactions occur between the functional groups and the hydrocarbon skeleton in a series of end-functionalized oligo(cyclohexylidenes) 1−12, their HeI photoelectron (PE) spectra were measured and analyzed. Vertical ionization energies, Ivj, of the highest occupied molecular orbitals (MOs) of 1−12 were assigned using ab initio RHF/6−31G* MO energies (−ϵj) in combination with Koopmans’ theorem. Excellent to good agreement was found between the PES and RHF/6−31G* results. In addition, the Ivj, assignments were further corroborated by a comparison of the PES data of 1−12 with those previously reported for appropriate reference compounds 13−20. To assess contributions from through-bond (TB) and/or through-space (TS) interactions, RHF/6−31G*/NBO analyses were performed. The results show that in the cases of 1−12, TS interactions do not occur. TB interactions were unequivocally identified for 1−4, 8, 10 and 11−12. These TB interactions were found to be relayed via the Hax−C−C−Hax precanonical σ-MOs (σ-PCMOs) of the cyclohexyl-like moieties.
Beschreibung:Gesehen am 27.10.2020
Beschreibung:Online Resource
ISSN:1099-0690
DOI:10.1002/1099-0690(200007)2000:14<2629::AID-EJOC2629>3.0.CO;2-6

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