The field of stable silylene research has grown dramatically since the first isolation of a stable silylene in 1994. Prior to 1994, silylenes existed only as reactive intermediates, isolable only in low-temperature matrixes. Since then, several stable silylenes have been synthesized, some in fact showing remarkable thermal stability. This Account highlights the developments in stable silylene chemistry, including theoretical and experimental studies attempting to explain the remarkable stability of the silylenes as well as the rapidly expanding reaction chemistry of the stable silylenes.
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.
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