Photo-initiated bromination of octakis(1,1,2-trimethylpropyl)octasila- cubane with tetrabromomethane

Bromination reactions of octasilacubane via radical intermediates are demonstrated. In the absence of oxygen, UV-light irradiation of octakis(1,1,2-trimethylpropyl)octasilacubane (1) with tetrabromomethane in benzene resulted in the formation of only exo,exo-4,8-dibromoctakis(1,1,2-trimethylpropyl)tetracyclo[3.3.0.0^2,7.0^3,6]octasilane(2). However, in the presence of oxygen, the reaction of 1 with tetrabromomethane took place without irradiation, producing 2 and a novel type of the monooxidation product, dibromooxahomosecocubane (3). For the formation of these products, an electron-transfer mechanism involving successive cleavage of the Si–Si bonds, followed by skeletal rearrangement is proposed.