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The occurrence of through-bond orbital interactions in an α,ω donor-acceptor substituted bi(cyclohexylidene) and bi(cyclohexyl): x-Ray diffraction, UV-Vis absorption and photoelectron spectroscopy, ab initio SCF-MO and natural bond orbital analyses

The ground state σ-π and π-π* interactions in 2-[4-(1-phenylpiperidin-4-ylidene)cyclohexylidene]malononitrile (1) and 2-[4-(1-phenylpiperidin-4-yl)cyclohexylidene]malononitrile (2) have been studied. Both the ionization potentials of 1 and 2, and ab initio RHF/6-31G calculations in combination with...

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Hauptverfasser: Oosterbaan, Wibren (VerfasserIn) , Havenith, Remco W. A. (VerfasserIn) , Walree, Cornelis A. van (VerfasserIn) , Jenneskens, Leonardus W. (VerfasserIn) , Gleiter, Rolf (VerfasserIn) , Kooijman, Huub (VerfasserIn) , Spek, Anthony L. (VerfasserIn)
Dokumenttyp: Article (Journal)
Sprache:Englisch
Veröffentlicht: 11th June 2001
In: Perkin
Year: 2001, Heft: 7, Pages: 1066-1074
ISSN:1364-5471
DOI:10.1039/B102410H
Online-Zugang:Resolving-System, lizenzpflichtig, Volltext: https://doi.org/10.1039/B102410H
Verlag, lizenzpflichtig, Volltext: https://pubs.rsc.org/en/content/articlelanding/2001/p2/b102410h
Volltext
Verfasserangaben:Wibren D. Oosterbaan, Remco W.A. Havenith, Cornelis A. van Walree, Leonardus W. Jenneskens, Rolf Gleiter, Huub Kooijman and Anthony L. Spek
Beschreibung
Zusammenfassung:The ground state σ-π and π-π* interactions in 2-[4-(1-phenylpiperidin-4-ylidene)cyclohexylidene]malononitrile (1) and 2-[4-(1-phenylpiperidin-4-yl)cyclohexylidene]malononitrile (2) have been studied. Both the ionization potentials of 1 and 2, and ab initio RHF/6-31G calculations in combination with a natural bond orbital analysis show that the ground state through-bond interaction (TBI) between the 1-phenylpiperidine electron donor and the dicyanoethylene electron acceptor in 1 and 2 is distinct but small. The olefinic bond in 1 enhances the interaction between the 1-phenylpiperidine electron donor and the dicyanoethylene electron acceptor as compared to 2. The TBI between the N,N-dialkylanilino donor and the olefinic bond in 1 can be modulated by rotation of the phenyl group around the C-N bond. The solid state structures of 1 and 2 have been determined by single crystal X-ray diffraction. In the crystal intermolecular electron-donor-acceptor complexes are formed, which give rise to an intermolecular charge transfer absorption in the solid state.
Beschreibung:Gesehen am 11.11.2020
Beschreibung:Online Resource
ISSN:1364-5471
DOI:10.1039/B102410H

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