Photoelektronenspektroskopische Untersuchung transanularer π-, σ- und n-Wechselwirkungen in brückenkopfsubstituierten Triptycenen
作者： Hans-Dieter Martin , Bernhard Mayer , Rolf Gleiter , Wolfgang Schäfer , Fritz Vögtle
关键词: Crystallography 、 Intramolecular force 、 Octane 、 Stereochemistry 、 Chemistry 、 Bicyclic molecule 、 Inorganic chemistry
摘要: Im Triptycen-System (1, 3, 4) werden photoelektronenspektroskopisch zwei Arten intramolekularer Wechselwirkungen beobachtet. Die longicyclische π,π-Homokonjugation ist von ahnlicher Grose wie in Cyclophanen. longitudinate Kopplung Bruckenkopfsubstituenten mittels geeigneter σ-Bindungen des Bicyclo[2.2.2]octan-Gerustes wird im 9,10-Dibromderivat 4 zu 0.25 eV abgeschatzt. Photoelectron Spectroscopic Investigation of Transanular π-, σ-, and n-Interactions Bridgehead Substituted Triptycenes Two kinds intramolecular interactions are observed triptycenes by PE-spectroscopy. The longicyclic π,π-homoconjugation turns out to be similar magnitude as cyclophanes. longitudinal coupling bridgehead substituents means suitable σ-bonds the bicyclo [2.2.2]octane skeleton amounts about 9,10-dibromotriptycene 4.
sci-hub.se 参考文章(16)
Fritz Vögtle, Gerd Hohner, Stereochemistry of multibridged, multilayered, and multistepped aromatic compounds — Transanular steric and electronic effects Organic Compunds. pp. 1- 29 ,(1978) , 10.1007/BFB0050144
Fritz Vögtle, Peter Neumann, [2.2]Paracyclophanes, structure and dynamics ChemInform. ,vol. 5, pp. 67- 129 ,(1974) , 10.1007/BFB0111431
Horst Prinzbach, Gottfried Sedelmeier, Carl Krüger, Richard Goddard, Hans-Dieter Martin, Rolf Gleiter, Eine ungewöhnliche Benzol/Benzol-„through-space”- Wechselwirkung Angewandte Chemie. ,vol. 90, pp. 297- 305 ,(1978) , 10.1002/ANGE.19780900423
K. Anzenhofer, J. J. de Boer, The crystal and molecular structure of triptycene, C20H14 Zeitschrift Fur Kristallographie. ,vol. 131, pp. 103- 113 ,(1970) , 10.1524/ZKRI.1970.131.1-6.103
F. Brogli, E. Heilbronner, The Competition between Spin Orbit Coupling and Conjugation in Alkyl Halides and its Repercussion on their Photoelectron Spectra Helvetica Chimica Acta. ,vol. 54, pp. 1423- 1434 ,(1971) , 10.1002/HLCA.19710540523
Hans-Dieter Martin, Peter Pföhler, Thomas Urbanek, Robin Walsh, Thermolyse von Ansaran, Ansaren und Cuban Chemische Berichte. ,vol. 116, pp. 1415- 1421 ,(1983) , 10.1002/CBER.19831160417
Edgar Heilbronner, John P. Maier, Consequences of Substitution in the Photoelectron Spectra of [2, 2]Paracyclophanes: Separation of ‘through‐space’ and ‘through‐bond’ interactions as a consequence of fluorosubstitution Helvetica Chimica Acta. ,vol. 57, pp. 151- 159 ,(1974) , 10.1002/HLCA.19740570113
V. Boekelheide, W. Schmidt, A photoelectron spectroscopic study of a classically conjugated but orbitally unconjugated tris-bridged cyclophane: [2.2.2.](1,3,5) cyclophane-1,9,17-triene Chemical Physics Letters. ,vol. 17, pp. 410- 413 ,(1972) , 10.1016/0009-2614(72)87109-4
E. Haselbach, E. Heilbronner, G. Schröder, The Interaction of π‐Orbitals in Barrelene Helvetica Chimica Acta. ,vol. 54, pp. 153- 162 ,(1971) , 10.1002/HLCA.19710540114
Edgar. Heilbronner, K. A. Muszkat, Applications of photoelectron spectroscopy. X. Relative importance of through-space vs. through-bond interaction between the lone pairs in 1,4-diazabicyclo[2.2.2]octane Journal of the American Chemical Society. ,vol. 92, pp. 3818- 3821 ,(1970) , 10.1021/JA00715A064