PHOTOCHEMISTRY OF DIMETHYLSILYL AZIDE - FORMATION AND REACTIVITY OF 1,1-DIMETHYLSILANIMINE

UV photolysis (248 nm) of matrix-isolated dimethylsilyl azide (Ic) lea ds to the formation of I,1-dimethylsilanimine (3c) and 1-(methylsilyl) methanimine (6c). The reactivity of the silanimine in the matrix was i nvestigated. Thermal reaction at 50 K yields the head-to-tail dimeriza tion product. Under the conditions of matrix isolation the silanimine proved to be stable toward oxidation and photooxidation with molecular oxygen and did not react with formaldehyde, carbon monoxide, and ammo nia, (Dimethylsilyl)nitrene (2c) as the primary photoproduct of the az ide could not be observed spectroscopically but was trapped with carbo n monoxide or with molecular oxygen, Upon photolysis at lambda = 193 n m methane and silyl isocyanide (Ia) are formed, The latter is the fina l product of a series of rearrangements of methylnitrilosilane (14), w hich is postulated to be the primary product of the 193 nm photolysis of the silanimine.