Methylated Dihydropentafulvalenes and Pentafulvalenides from Tetramethylcyclopentadiene Derivatives

Abstract

Treatment of tetramethylcyclopentadienyllithium (1Li) with CuCl₂ or bromotetramethylcyclopentadiene (4), respectively, as well as reaction of stannylated tetramethylcyclopentadiene with 4 in presence of PdBr₂ gave two isomeric octamethyldihydropentafulvalenes (3 and 5), of which 5 was deprotonated to a highly substituted cyclopentadienyl anion. Conversion of 1Li to iodotetramethylcyclopentadiene (7) and reaction of 7 with cyclopentadienyl anion yielded three tautomers of tetramethyldihydropentafulvalene (8a, 8b,and 8c) or exclusively 8a depending on the conditions. The crystal structures of 3 and 8a have been determined, and the isomers of 8 have been converted into the corresponding dianion.

Key words

dihydropentafulvalenes - bicyclopentadiendiyl dianion - coupling - cyclopentadienes - lithiation

References

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Further data may be obtained on request from The Director, Cambridge Crystallographic Data Centre, Lensfield Road, Cambridge CB2 1EW, UK by quoting the number CCDC 149911.

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Fachinformationszentrum Karlsruhe, 76344 Eggenstein-Leopoldshafen, Germany by quoting the number CSD 405749.