Acyclic and cyclic silylazines and azinylsilanes

C-lithiated bis(tert-butyl-methyl)ketazine reacts with halosilanes to give the monosilylketazines, t-Bu(Me)C=N-N=C(t-Bu)-CH2R, (1-7). (1: R = SiMe3; 2: R = SiClMe2; 3: R = SiClMePh; 4: R = Cl2SiPh; 5: R = SiCl3; 6: R = SiMe2Ph; 7: R = F2SiN(t-Bu)SiMe3). The bis(ketazinyl)silanes [t-Bu(RCH2) C = N-N = CCH2-t-Bu](2) SiMe2 8, 9 are formed in the reaction of the same lithiated ketazine or 1 with Cl2SiMe2 in a molar ratio of 2:1, (8: R = H; 9: R = SiMe3). Di(silyl)ketazines (10, 11) are obtained from lithiated 1 and ClSiMe2Ph in a molar ratio of 1:1 and from dilithiated ketazine with F2Si(i-Pr)(2) in a molar ratio of 1:2 [t-Bu(RH2C)C=N-N=C(CH2R')t-Bu, 10: R = SiMe3, R' = SiMe2Ph; 11: R,R' = FSi(i-Pr)(2)]. The tris(ketazinyl)fluorosilane 12 is isolated from the reaction of SiF4 with the lithiated ketazine. 2-Alkenyl-1,2-diaza-3-sila-5-cyclopentenes, t-Bu(CH2)C-[N-SiR,R'-CH2-C(t-Bu)=N], (14-17) are obtained from the dilithiated ketazine and Hal(2)SiRR'. (14: Hal = Cl, R = Me, R' = Ph; 15: Hal = F, R = t-Bu, R' = Ph; 16: Hal = F, R = t-Bu, R' = F; 17: Hal = F, R = N(t-Bu)SiMe3, R' = F). X-ray structure analyses are presented for 7, 11, and 17.