Synthesis, Characterization, and Structural Analysis of AM[Al(NON^Dipp)(H)(SiH₂Ph)] (AM = Li, Na, K, Rb, Cs) Compounds, Made Via Oxidative Addition of Phenylsilane to Alkali Metal Aluminyls

We report the oxidative addition of phenylsilane to the complete series of alkali metal (AM) aluminyls [AM{Al(NON^Dipp)}]₂ (AM = Li, Na, K, Rb, and Cs). Crystalline products (1-AM) have been isolated as ether or THF adducts, [AM(L)_n][Al(NON^Dipp)(H)(SiH₂Ph)] (AM = Li, Na, K, Rb, L = Et₂O, n = 1; AM = Cs, L = THF, n = 2). Further to this series, the novel rubidium rubidiate, [{Rb(THF)₄}₂(Rb{Al(NON^Dipp)(H)(SiH₂Ph)}₂)]⁺ [Rb{Al(NON^Dipp)(H)(SiH₂Ph)}₂]^-, was isolated during an attempted recrystallization of Rb[Al(NON^Dipp)(H)(SiH₂Ph)] from a hexane/THF mixture. Structural and spectroscopic characterizations of the series 1-AM confirm the presence of μ-hydrides that bridge the aluminum and alkali metals (AM), with multiple stabilizing AM···π(arene) interactions to either the Dipp- or Ph-substituents. These products form a complete series of soluble, alkali metal (hydrido) aluminates that present a platform for further reactivity studies.