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Reactions of the lithium salts of the tert-butylmethylhydrazones Me 3 C(Me)C=N-NLiR, (R = H, Me, CMe 3 ) with fluorosilanes and -boranes in a molar ratio 1 : 1 gave the silyl- (1 - 3, 5, 6) and borylhydrazones (4, 8) Me 3  C(Me)C=N-N(R)Rʹ; 1: R = H, Rʹ = SiFMe 2  ; 2: R = H, Rʹ = SiMe 2 CMe 3 ; 3: R = H, Rʹ = SiF(CMe 3  ) 2 ; 4: R = H, Rʹ = BFN(SiMe 3 ) 2 ; 5: R = Me 3  C, Rʹ = SiF 2 CMe 3 ; 6: R = Me 3 C, Rʹ = F 2 SiC(SiMe 3 ) 3 ; 8: R = Me 3 C, Rʹ = BFN(SiMe 3 ) 2 . The lithiated hydrazone Me 2 C=N-NH(Me) reacted with F 3 SiC(SiMe 3 ) 3  to give the silylhydrazone Me 2 C=N- NHSiF 2 C(SiMe 3 ) 3 , 7. Because of the fluoro functionality of 1 and 4, the bis-hydrazonylsilane 9 and the bis- and tris-hydrazonylboranes 10 and 11 could be synthesised, (Me 3 C(Me)C=N-NH) 2 R; 9: R = SiMe 2  , 10: R = BN(SiMe 3 ) 2 ; 11: (Me 3 C(Me)C=N-NH) 3 B. Starting from 2 and its lithium salt, secondary substitutions are possible. Bis(silyl)- and silyl(boryl)hydrazones are formed (12 - 15); Me 3 C(Me)C=N(R) (SiMe 2 CMe 3 ) 12: R = SiFMe 2 ; 13: R = SiF(CMe 3 ) 2 ; 14: R = SiF 2 CMe 3 ; 15: R = BFN(SiMe 3  ) 2 . Ring closure occurs in the reaction of dilithiated Me 2 C=N- NHCMe 3  with F 2 Si(CHMe 2 ) 2 . The 1,2-diaza-3-sila-5-cyclopentene 16 is isolated. The fluorofunctional silyl-hydrazones 7, 12, and 13 cyclise in reactions with t-BuLi to give 1,2-diaza-3-sila-5- cyclopentenes 17 - 20; RN(N=CRʹ-CH 2 )Rʺ; 17: R =Me,Rʹ = Me 3 C, Rʺ = SiFC(SiMe 3 ) 3 ; 18: R = Me 3 C, Rʹ = SiMe 2 CMe 3 , Rʺ = SiMe 2 ; 19: R =Me 3 C, Rʹ = SiMe 2 CMe 3 , Rʺ = Si(CMe 3 ) 2 . A 1,2- diaza-3-bora-5-cyclopentene 20 is the result of the reaction of 8 with t-BuLi: Me 3 CN(N=CCMe 3 - CH 2 )BN(SiMe 3 ) 2 . The H-acidic methylene group of the five-membered ring in 20 can be lithiated with n-BuLi and substituted with fluorosilanes. Starting from 16 and 20, the silyl-substituted rings Me 3 CN(N=CMe-CHR)Si(CHMe 2 ) 2  21 - 23 and 25 are obtained; 21: R = SiMe 3 ; 22: R = SiF 2 C(SiMe 3 ) 3 ; 23: R = SiF 3 ; 25: Me 3 CN[N=CC(Me) 3 CHSiMe 3 ]BN(SiMe 3 ) 2 . Using SiF 4  as fluorosilane, the main product is the difluorosilane containing two rings; F 2 Si[CHC(Me)=N-NCMe 3 - Si(CHMe 2 ) 2 ] 2 . The methine group in 4-position of the silyl-substituted rings is also acidic and reacts with n-BuLi to give lithium salts which react with aminodifluoroboranes giving the ring compounds Me 3 CN[N=C(CMe 3 )C(SiMe 2 R)(FBNRʹ SiMe 3 )]SiMe 2  26 - 28; 26: R = Me, Rʹ = CMe 3 ; 27: R = F, Rʹ = CMe 3  ; 28: R = F, Rʹ = SiMe 3 . In contrast to the substitution reactions of fluorosilanes with lithiated rings, an unusual oxidation reaction occurs starting from lithiated Me 3 CN(N=C(CMe 3 )CH 2 )Si(CHMe 2 ) 2  and ClSiMe 2 CMe 3  to give 29, in which a C-C bond in 4- position links two five-membered rings. The disilane (Me 3 CSiMe 2 ) 2  is formed as a by-product of this reaction. The combination of the N-SiF 2 CMe 3 -substituted hydrazones 5 and 14 with t-BuLi in a molar ratio 1 : 2 leads to the colourless, crystalline tricyclic products 30 and 31 which are dimeric 1,2-diaza-3-sila-3,5-cyclopentadienes. The molecular structures of 3, 6, 11, 30, and 31 are reported.

Synthese und Cyclisierung von Boryl- und Silylhydrazonen / Synthesis and Cyclisation of Boryl- and Silylhydrazones