Carbene chemistry. Part III. Reactions of diazomethyltrimethylsilane

Abstract

Photolysis of diazomethyltrimethylsilane yields nitrogen and trimethylsilycarbene (Me₃Si·[graphic omitted]H), which reacts with diazomethyltrimethylsilane, trans-but-2-ene, and ethylene to give trans-2,2,5,5-tetramethyl-2,5-disilahex-3-ene, trans-1,2-dimethyl-3-trimethylsilylcyclopropane, and trimethylsilycyclopropane, respectively. The carbene does not react with 2,3-dimethylbut-2-ene to form a cyclopropane, but undergoes insertion (i) into the Si–H bond of trimethylsilane to give 2,2,4,4-tetramethyl-2,4-disilapentane, (ii) into a C–H bond of hexamethyldisiloxane to give 2,2,4,4,7,7-hexamethyl-3-oxa-2,4,7-trisilaoctane, and (iii) into the Si–H bond or a C–H bond of 2,2,4,6,6-pentamethyl-3,5-dioxa-2,4,6-trisilaheptane to give 2,2,4,6,6-pentamethyl-4-trimethylsilylmethyl-3,5-dioxa-2,4,6-trisilaheptane and 2,2,4,6,6,9,9-heptamethyl-3,5-dioxa-2,4,6,9-tetrasiladecane, respectively.