WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow G1 1XL, U.K.
School of Chemical and Physical Sciences, Victoria University of Wellington, P.O. Box 600, Wellington 6140, New Zealand.
Inorg Chem. 2022 Dec 12;61(49):19838-19846. doi: 10.1021/acs.inorgchem.2c03010. Epub 2022 Nov 23.
We report the oxidative addition of phenylsilane to the complete series of alkali metal () aluminyls [{Al(NON)}] ( = Li, Na, K, Rb, and Cs). Crystalline products () have been isolated as ether or THF adducts, [(L)][Al(NON)(H)(SiHPh)] ( = Li, Na, K, Rb, L = EtO, = 1; = Cs, L = THF, = 2). Further to this series, the novel rubidium rubidiate, [{Rb(THF)}(Rb{Al(NON)(H)(SiHPh)})] [Rb{Al(NON)(H)(SiHPh)}], was isolated during an attempted recrystallization of Rb[Al(NON)(H)(SiHPh)] from a hexane/THF mixture. Structural and spectroscopic characterizations of the series confirm the presence of μ-hydrides that bridge the aluminum and alkali metals (), with multiple stabilizing ···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.
我们报道了芳基硅烷与完整系列碱金属（）铝化物 [{Al(NON)}]（=Li、Na、K、Rb 和 Cs）的氧化加成反应。已将作为醚或 THF 加合物分离出结晶产物 ()，[(L)][Al(NON)(H)(SiHPh)]（=Li、Na、K、Rb、L=EtO、=1；=Cs、L=THF、=2）。在此系列的基础上，在试图从己烷/THF 混合物中重结晶 Rb[Al(NON)(H)(SiHPh)]时，分离出了新型铷铷化物 [{Rb(THF)}(Rb{Al(NON)(H)(SiHPh)})][Rb{Al(NON)(H)(SiHPh)}]。对该系列的结构和光谱表征证实了 μ-氢化物的存在，该氢化物桥接铝和碱金属（），并与 Dipp-或 Ph-取代基形成多个稳定的···π（芳族）相互作用。这些产物形成了完整的可溶性碱金属（氢化物）铝酸盐系列，为进一步的反应性研究提供了平台。
