Thermal and Photochemical Cleavage of SiSi Double Bond in Tetrasila-1,3-diene

A novel stable tetrasila-1,3-diene 3 was synthesized by the reduction with sodium of the corresponding 1,2,2-tribromodisilane. X-ray analysis shows that the tetrasila-1,3-diene skeleton of 3 is highly twisted but adopts an anticlinal conformation in contrast to the previously reported tetrasila-1,3-dienes showing a synclinal conformation. Upon heating at 80 °C or irradiation using filtered light (λ > 390 nm) of 3 in benzene, clean dissociation of one of the SiSi double bonds of 3 occurred to give a novel cyclotrisilene 4 together with silylene 2 suggesting the initial SiSi double bond dissociation of 3 to the corresponding disilenylsilylene 8 and silylene 2; cyclotrisilene 4 would be formed by the intramolecular silylene insertion into the SiSi bond of 8.