Synthesis, Characterization, and Structural Analysis of AM [Al(NON Dipp )(H)(SiH 2 Ph)] ( 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)(SiH 2 Ph)] ( AM = Li, Na, K, Rb, L = Et 2 O, 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)(SiH 2 Ph)} 2 )] + [Rb{Al(NON Dipp )(H)(SiH 2 Ph)} 2 ] - , was isolated during an attempted recrystallization of Rb[Al(NON Dipp )(H)(SiH 2 Ph)] 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.