Long-range σ−π interactions in tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes): photo-electron spectroscopy, ab initio SCF MO calculations, and natural bond orbital analyses
Long-range σ−π interactions in tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes) were identified by He(I) photoelectron spectroscopy (PES) and ab initio RHF/6-31G* calculations. The vertical ionization energies Iv,j of the highest occupied molecular orbitals (MO's) were assigned using...
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| Hauptverfasser: | , , , , , , , |
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| Dokumenttyp: | Article (Journal) |
| Sprache: | Englisch |
| Veröffentlicht: |
06/24/2000
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| In: |
The journal of organic chemistry
Year: 2000, Jahrgang: 65, Heft: 15, Pages: 4584-4592 |
| ISSN: | 1520-6904 |
| DOI: | 10.1021/jo000199y |
| Online-Zugang: | Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1021/jo000199y Verlag, lizenzpflichtig, Volltext: https://pubs.acs.org/doi/10.1021/jo000199y 
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| Verfasserangaben: | Albert W. Marsman, Remco W.A. Havenith, Sabine Bethke, Leonardus W. Jenneskens, Rolf Gleiter, Joop H. van Lenthe, Martin Lutz, and Anthony L. Spek |
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| 520 | |a Long-range σ−π interactions in tetrahydro-4H-thiopyran end-capped oligo(cyclohexylidenes) were identified by He(I) photoelectron spectroscopy (PES) and ab initio RHF/6-31G* calculations. The vertical ionization energies Iv,j of the highest occupied molecular orbitals (MO's) were assigned using Koopmans' theorem (Iv,j = −εj) and by correlation with the ionizations of related reference compounds. The experimental (PES) and theoretical (RHF/6-31G*) results are in good agreement. For tercyclohexylidene derivatives which contain two nonconjugated π-bonds splittings ΔIv,j of the π-bands in the range from ∼0.5 to 0.7 eV (Δ−εj ∼0.6 to 0.9 eV). For the bi- and tercyclohexylidene compounds containing two sulfur atoms at their α- and ω-end positions the π-type sulfur lone pair bands [Lpπ(S)] split significantly by ΔIv,j ∼0.3 to 0.4 eV (Δ−εj ∼0.3 to 0.4 eV), i.e. σ−π interactions over distances of ca. 8 and 12 Å, respectively, occur. The magnitude of the interactions and the observed splittings are independent of the anti and syn conformations of the oligo(cyclohexylidene) hydrocarbon skeletons. RHF/6-31G* Natural Bond Orbital analyses reveal that the Hax−C−C−Hax precanonical MO's (PCMO's) centered on the cyclohexyl-type rings are paramount for the relay of the through-bond σ−π interactions; no through-space σ−π interactions were identified. | ||
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