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Trialkylsilyl-Substituted Silole and Germole Dianions

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posted on 03.12.2018, 16:05 by Zhaowen Dong, Crispin R. W. Reinhold, Marc Schmidtmann, Thomas Müller
The synthesis of dipotassio-2,5-bis­(trialkylsilyl)­silacyclopentadienediides K2[3] and germacyclopentadienediides K2[4] is reported. The prepared silole dianions, 3, are characterized by a significantly deshielded silicon nuclei with 29Si NMR signals at very unusual low field positions for silicon anions (δ29Si = 148–169). The results of DFT calculations revealed that this deshielding is a consequence of the silylene-like frontier orbitals of silole dianions 3 and efficient hyperconjugation between the trialkylsilyl-substituents and the cyclic delocalized π-system. Solid-state structure determinations of potassium salts of silole and germole dianions revealed a novel polymeric bis-η5,bis-η1-coordination mode between heterole and potassium ions.

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