(PhC(NtBu)

A silicon-aluminum heterocycle LAl(SiH2SiH2)2AlL (L = PhC(NtBu)2) (1) was prepared. Compound 1 exhibits a unique (N2Al)2(SiH2)4 centrosymmetric six-membered ring structure with a chair conformation, which is comparable with that of cyclohexane. Furthermore, two intermediate analogues, silylene-alane adduct LSi(AlMe3)-Si(AlMe3)L (2) and silylene-alane oxidative product [LAlHSiH2Mes]2 (3) were obtained. Compound 3 has an interesting arrangement of an Al-H and an SiH2 unit, which are in close vicinity to each other. 3 might be important to function as a catalyst, due to the already activated bridging Al-H bonds.