Through-bond orbital coupling in end-functionalized bicyclohexylidenes

• Verfasst von: Marsman, Albert W. [VerfasserIn]
• Verfasst von: Havenith, Remco W. A. [VerfasserIn]
• Verfasst von: Bethke, Sabine [VerfasserIn]
• Verfasst von: Jenneskens, Leonardus W. [VerfasserIn]
• Verfasst von: Gleiter, Rolf [VerfasserIn]
• Verfasst von: Lenthe, Joop H. van [VerfasserIn]
• Titel: Through-bond orbital coupling in end-functionalized bicyclohexylidenes
• Titelzusatz: photoelectron spectroscopy and ab initio SCF-MO calculations
• Verf.angabe: Albert W. Marsman, Remco W. A. Havenith, Sabine Bethke, Leonardus W. Jenneskens, Rolf Gleiter, and Joop H. van Lenthe
• E-Jahr: 2000
• Jahr: 07 September 2000
• Umfang: 13 S.
• Teil: year:2000
• Teil: number:14
• Teil: pages:2629-2641
• Teil: extent:13
• Fussnoten: Gesehen am 27.10.2020
• Titel Quelle: Enthalten in: European journal of organic chemistry
• Ort Quelle: Weinheim : Wiley-VCH Verl., 1998
• Jahr Quelle: 2000
• Band/Heft Quelle: (2000), 14, Seite 2629-2641
• ISSN Quelle: 1099-0690
• DOI: doi:10.1002/1099-0690(200007)2000:14<2629::AID-EJOC2629>3.0.CO;2-6
• Datenträger: Online-Ressource
• Sprache: eng
• Sach-SW: Ab initio calculations
• Sach-SW: Oligo(cyclohexylidenes)
• Sach-SW: Photoelectron spectroscopy
• Sach-SW: Through-bond interactions
• Sach-SW: Through-space interactions
• K10plus-PPN: 1736660683

Abstract

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.