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Selenium- and tellurium-bridged heteromerous overcrowded bistricyclic aromatic enes with central six-member and seven-member rings

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Abstract

A series of selenium-bridged and tellurium-bridged heteromerous bistricyclic aromatic enes (BAEs) 15–25 with six-member and seven-member central rings have been synthesized by Barton–Kellogg olefination, twofold extrusion coupling method between tricyclic aromatic thiones and tricyclic aromatic diazo derivatives. The crystal structures of thioxanthenylidene-anthracenone (15), selenoxanthenylidene-anthracenone (20), and telluroxanthenylidene-anthracenone (21) were determined. The ordered crystal structure of 21 showed a very high degree of folding of the telluroxanthenylidene moiety (58.5°) and very short intramolecular Te···C9′ contact distance, indicating >20 % penetration which may reflect secondary nonbonding interactions and lack of aromatic telluroxanthenylium-anthracenolate contribution. The BAEs were subjected to a 1H-, 13C-, 77Se-, and 125Te-NMR spectroscopic study. The 1H-NMR spectra indicated anti-folded conformations in solution. The measured pronounced downfield 77Se- and 125Te-NMR shifts in 20 and 21, relative to the corresponding spectra of homomerous BAEs diselenoxanthylene (7) and ditelluroxanthylene (8), may be due to the proximity of the Se and Te bridges to the carbons of the central enes in the anti-folded conformations. This deshielding effect was larger in 21 than in 20, δ(125Te)/δ(77Se) = 1.53, a ratio higher than in any other member of the series.

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Authors and Affiliations

  1. Organic Chemistry, Institute of Chemistry, The Hebrew University of Jerusalem, Philadelphia Building #201/205, Edmond J. Safra Campus, 91904, Jerusalem, Israel

    Amalia Levy, Shmuel Cohen, Sergey Pogodin & Israel Agranat

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  1. Amalia Levy
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  2. Shmuel Cohen
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  3. Sergey Pogodin
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  4. Israel Agranat
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Correspondence to Israel Agranat.

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This paper is dedicated to Professor Magdolna Hargittai, a structural scientist par excellence, on occasion of her 70th birthday.

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Levy, A., Cohen, S., Pogodin, S. et al. Selenium- and tellurium-bridged heteromerous overcrowded bistricyclic aromatic enes with central six-member and seven-member rings. Struct Chem 26, 1565–1584 (2015). https://doi.org/10.1007/s11224-015-0675-8

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