Polylithiumkomplexe aus phenylsubstituierten 1,6,6aλ4‐Trithiapentalenen und verwandten Verbindungen und Lithium

Phenylsubstituierte 1,6,6aλ4-Trithiapentalene (1a – d) und 3H-1,2-Dithiol-3-thione (2a, b), 2-(4-Phenyl-3H-1,2-dithiol-3-yliden)acetophenon (3) und 1,5-Diphenyl-1,3,5-pentantrion (4) reagieren in Tetrahydrofuran oder 2-Methyltetrahydrofuran bei 0°C mit 7 – 10 Li/mol zu hochreaktiven, loslichen Polylithiumkomplexen, die durch Ausfallung mit Pentan als Feststoffe der Zusammensetzung ALi7–10 · THF, A = Ausgangsverbindung, isoliert werden konnen. Fur den aus 1a und 10 Li in THF erhaltlichen Polylithiumkomplex wurde aufgrund der Reaktion mit Wasser bzw. Methyliodid, Pentacen und Wasserstoff die Konstitution 5a vorgeschlagen. Die Annahme, das in 5a und in dem vergleichbaren Komplex 5b (aus 1b und 9 Li) Li2S-Molekule komplexgebunden sind, wird insbesondere durch 7Li- und 1H-NMR-Messungen an festem 5b unterstutzt. Polylithium Complexes from Phenyl-substituted 1,6,6aλ. Trithiapentalenes and Related Compounds and Lithium Phenyl-substituted 1,6,6a⋋LD4-trithiapentalenses (1a – d) and 3H-1,2-dithiole-3-thiones (2a, b), 2-(4-phenyl-3H-1,2-dithiol-3-ylidene)acetophenone (3), and 1,5-diphenyl-1,3,5-pentanetrione (4) react in tetrahydrofuran or 2-methyltetrahydrofuran at 0°C with 7 – 10 Li/mol to form highly reactive, soluble polyithium complexes. These can be precipitated from solution by addition of pentane and have the composition A Li7–10 · THF, where A = starting compound. The polylithium complex obtained from 1a and 10 Li is suggested to have the constitution 5a on the basis of reaction with water, methyl iodide, pentacene, and hydrogen, respectively. The assumption that 5a and the analogous complex 5b (formed by reacting 1b and 9 Li) contain Li2S molecules in complexed form is supported in particular by solid state 7Li and 1H NMR measurements.

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