Photoinduced Brook-Type Rearrangement of Acylcyclopolysilanes

[Image: see text] Previously unknown 1,1,4-tris(trimethylsilyl)-4-acyldodecamethylcyclohexasilanes (Me(3)Si)(2)Si(6)Me(12)(Me(3)Si)COR (16a, R = tert-butyl; 16b, R = 1-adamantyl) have been synthesized by the reaction of the potassium silanides (Me(3)Si)(2)Si(6)Me(12)(Me(3)Si)K with acid chlorides ClCOR, and their photochemical rearrangement reactions have been studied. The molecular structures of 16a,b as determined by single-crystal X-ray diffraction analysis exhibit an unusual twist-boat conformation of the cyclohexasilane ring. When 16a,b were photolyzed with λ >300 nm radiation, they underwent Brook type 1,3-Si → O migration reactions to generate the cyclohexasilanes 17a,b with exocyclic Si=C bonds along with smaller amounts of the ring-enlarged species 19a,b with endocyclic Si=C double bonds. While 17a,b were stable enough to allow characterization by NMR and UV absorption spectroscopy, the less stable products 19a,b could only be observed in the form of their methanol adducts.