Issue 7, 2001
From the journal:

Journal of the Chemical Society, Perkin Transactions 2

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†

Wibren D. Oosterbaan,a   Remco W. A. Havenith,ab   Cornelis A. van Walree,a   Leonardus W. Jenneskens,*a   Rolf Gleiter,c   Huub Kooijmand  and  Anthony L. Spekd  

* Corresponding authors

a Debye Institute, Department of Physical Organic Chemistry, Utrecht University, Padualaan 8, Utrecht, The Netherlands
E-mail: jennesk@chem.uu.nl
Fax: +31-302534533
Tel: +31-302533128

b Debye Institute, Theoretical Chemistry Group, Utrecht University, Padualaan 8, Utrecht, The Netherlands

c Institute of Organic Chemistry, University of Heidelberg, Im Neuenheimer Feld 270, Heidelberg, Germany

d Bijvoet Center for Biomolecular Research, Crystal and Structural Chemistry, Utrecht University, Padualaan 8, Utrecht, The Netherlands

Abstract

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.

Graphical abstract: 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

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Article information

DOI
https://doi.org/10.1039/B102410H
Article type
Paper
Submitted
14 Mar 2001
Accepted
15 May 2001
First published
11 Jun 2001

J. Chem. Soc., Perkin Trans. 2, 2001, 1066-1074

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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

W. D. Oosterbaan, R. W. A. Havenith, C. A. van Walree, L. W. Jenneskens, R. Gleiter, H. Kooijman and A. L. Spek, J. Chem. Soc., Perkin Trans. 2, 2001, 1066 DOI: 10.1039/B102410H

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