Reactivity Studies of Heteroleptic Silylenes PhC(NtBu)2SiX (X = NPh2, NMe2) toward Selected Azides

The reaction of LSiX (L = PhC­(NtBu)2, X = NPh2 (1), NMe2 (2)) with trimethylsilyl azide (3) resulted in silaimines [LSi­(NSiMe3)­X] (X = NPh2 (5), NMe2 (7)). Similarly the reaction of 1 and 2 with adamantyl azide (4) yielded [LSi­(NAd)­X] (X = NPh2 (6), NMe2 (8), Ad = adamantyl) compounds. Silaimines 5–8 contain tetracoordinate silicon atoms. Compounds 6 and 8 are the first tetracoordinate silicon compounds having the terminal SiNAd unit. All compounds were characterized by spectroscopic and spectrometric techniques. The molecular structures of 5, 6, and 8 were unequivocally established by single-crystal X-ray structure analysis.