The new germandiyls 1 and 2 which sublime at 50 °C are monomeric in the solid state, in solution, and in the gas phase. They are available from germanium dichloride · 1,4‐dioxane and the appropriate lithium diamides in high yields, and react smoothly with [Ni(CO)4] to give 3 and 4. According to ab initio calculations, the π electrons in 2 are delocalized. cod = cyclooctadiene.
The synthesis and several reactions of the stable silylene 1 (1,3-di-tert-butyl-2,3-dihydro-1H-1,3,2diazasilol-2-ylidene) are described. X-ray crystal structures are given for two intermediates in the synthesis of 1, the diimine 7 and its dilithium salt 8, and for a byproduct, the spiro compound 10. 1 reacts with ethanol and water by inserting into the O-H bond, and with iodomethane by insertion into the C-I bond. The silanol from reaction of 1 with water condenses to a disiloxane, 13. From 1 and sulfur and selenium, cyclic compounds containing Si 2 E 2 rings are obtained (E ) S or Se). Crystal structures are presented for disiloxane 13 and for the sulfur and selenium cycloadducts, 15 and 17.
Two tert‐butyl groups at the nitrogen atoms of the cyclic carbene 2, which is accessible from 1 by reduction with potassium, provide sufficient stability to enable it to be stored indefinitely under exclusion of air and moisture. In contrast, sterically less shielded carbenes of type 2 (R = Me, Et, iPr) dimerize slowly at room temperature to olefins 3.
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