Synthesis, characterisation and structural analysis of AM[Al(NONDipp)(H)(SiH2Ph)] (AM = Li, Na, K, Rb, Cs) compounds, made via oxidative addition of phenyl silane to alkali metal aluminyls

Ballmann, Gerd M. and Evans, Matthew J. and Gentner, Thomas X. and Kennedy, Alan R. and Fulton, J. Robin and Coles, Martyn P. and Mulvey, Robert E. (2022) Synthesis, characterisation and structural analysis of AM[Al(NONDipp)(H)(SiH2Ph)] (AM = Li, Na, K, Rb, Cs) compounds, made via oxidative addition of phenyl silane to alkali metal aluminyls. Inorganic Chemistry, 61 (49). pp. 19838-19846. ISSN 0020-1669 (https://doi.org/10.1021/acs.inorgchem.2c03010)

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Abstract

We report the oxidative addition of phenylsilane to the complete series of alkali metal (AM) aluminyls [AM{Al(NONDipp)}]2 (AM = Li, Na, K, Rb, and Cs). Crystalline products (1-AM) have been isolated as ether or THF adducts, [AM(L)n][Al(NONDipp)(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(NONDipp)(H)(SiH2Ph)}2)]+ [Rb{Al(NONDipp)(H)(SiH2Ph)}2]-, was isolated during an attempted recrystallization of Rb[Al(NONDipp)(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.