Three highly coordinated dichlorosilanes, 11 a, 12, and 13, were synthesized, and their structures were investigated in solution as well as in the solid state (12 and 13). The reductive dehalogenation of 11 a and 12 with magnesium yielded cyclotrisilanes 14 and 20, which are in equilibrium with silylenes 15 and 24 as shown by trapping and silylene-exchange experiments. Treatment of 13 with magnesium metal afforded a mixture of benzosilacyclobutene 38 and disilane 40, which also was obtained by the thermolysis of silacyclopropane 44. Trapping experiments corroborated the involvement of silylene 43 in these reactions.

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The ortho-lithiated aryl compounds [2-Me2NCH2-4,6-(Me)2C6H2]2Li2·OEt2 (2) and [2-Me2N(Me)NC6H4]2Li2·TMEDA (6) have been prepared by metalation of the corresponding precursors 1 and 5. 6 is the first aryllithium derivative bearing a hydrazino group as coordinating ortho-substituent. Both organolithium compounds form in the solid a dimeric aggregate as shown by X-ray diffraction. The seven-line 13C NMR signal (1 J(7Li−13C) = 20 Hz) of the ipso-carbon atoms of 6 is in agreement with a dimeric structure of this compound in solution (C6D6) as well.

Introduction Hydridosilyl Anions Alkyl‐Substituted Silyl Anions Aryl‐Substituted Silyl Anions Silyl‐Substituted Silyl Anions Functionalized Silyl Anions Miscellaneous