Acyclic and Cyclic Silylaminohydrazines

Abstract

The reaction of H(2)N-NH(2) with ClSiMe(2)N(SiMe(3))(2) in a molar ratio 1 : 2 gave the bis(silylamino) hydrazine HNSiMe(2)-N(SiMe(3))(2) (1). Compound 1 forms a monomeric dilithium salt with BuLi. From n-hexane (Me(3)Si-NSiMe(2)-NLiSiMe(3))(2) (2) crystallizes while from THF Me(3)Si-NSiMe(2)-NLi(THF)SiMe(3) (3) precipitates. Compounds 2 and 3 are formed from 1 via a silyl group migration. In the rearranged salts, the silyl groups are bonded at the hydrazino nitrogen atoms. Hydrolysis of 2 led to the formation of (Me(3)Si-N-SiMe(2)-NHSiMe(3))(2) (4) which is a structural isomer of 1. Ring closure occurs in reactions of 2 or 3 with F(3)B. OEt(2) or SiF(4). The seven-membered rings (Me(3)Si-N-SiMe(2)-NSiMe(3))(2)BF (5) and (Me(3)Si-NSiMe(2)-NSiMe(3))(2)SiF(2), (6) were isolated as the products. The crystal structures of 2, 3 and 5 have been determined.