[2+2]Cycloaddition Products of Tetradehydrodianthracene: Experimental and Theoretical Proof of Extraordinary Long C-C Single Bonds

Angewandte Chemie (International Edition in English)

Volumn 36, Issue 16, 1997, Pages 1757-1760

  Kammermeier, Stefan ^a   Jones, Peter G ^a   Herges, Rainer ^a  

^a TECHNICAL UNIVERSITY OF BRAUNSCHWEIG   (Germany)

Author keywords

Anthracene dimers; Cycloadditions; Density functional calculations; Raman spectroscopy; Strained molecules

Indexed keywords

EID: 0030870475     PISSN: 05700833     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.199717571     Document Type: Article

References (40)

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13. Compounds 2 and 3 are stable in solution at temperatures below 80°C. At higher temperatures slow decomposition was observed. The products were not further characterized.
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15. The same argument was used to explain the remarkable stability of the parent system didehydrodianthracene towards electrocyclic ring opening: a) R. B. Woodward, R. Hoffmann, The Conservation of Orbital Symmetry, Verlag Chemie, 1970, p. 54; b) N. M. Weinshenker, F. D. Greene, J. Am. Chem. Soc. 1968, 90, 506.
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32. To work with reasonable computational costs we replaced the dichloronaphthlene unit of dichloro-1,1,2,2-tetraphenylcyclobuta[b]naphthalene of Toda et al. by benzene. According to a PM3 calculation the bond length of the long C-C bond changes only insignificantly from 1.6778 to 1.6703 Å.
33. Analytical gradients and numerical second derivatives of the energy to the bond length C1-C2.
34. We thank Dr. Schiel of the Physikalisch-Technische Bundesanstalt, Braunschweig, for recording the Raman spectrum.
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38. 2v). Therefore there are several normal vibrations with a varying contribution of the C1-C2 stretching vibration.
39. 2,5]tetradeca-3,5,7,9,11,13-hexaene as a model system. It corresponds to structure 3 in which the four benzene rings of the didehydrodianthracene framework are replaced by double bonds. A harmonic frequency analysis with the PM3 approximation and the Becke3LYP/6-31G* method was performed. A scaling factor of 0.948 for the PM3 method was determined by comparing the four normal modes with the largest contribution of the C-C stretching trajectory. The length of the corresponding C-C bond in the model system at the Becke3LYP/6-31G* level was 1.784 Å.
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