Three Oxidative Addition Routes of Alkali Metal Aluminyls to Dihydridoaluminates and Reactivity with CO 2

Three distinct routes are reported to the soluble, dihydridoaluminate compounds, AM[Al(NON Dipp )(H) 2 ] (AM=Li, Na, K, Rb, Cs; [NON Dipp ] 2− =[O(SiMe 2 NDipp) 2 ] 2− ; Dipp=2,6‐ i Pr 2 C 6 H 3 ) starting from the alkali metal aluminyls, AM[Al(NON Dipp )]. Direct H 2 hydrogenation of the heavier analogues (AM=Rb, Cs) produced the first examples of structurally characterized rubidium and caesium dihydridoaluminates, although harsh conditions were required for complete conversion. Using 1,4‐cyclohexadiene (1,4‐CHD) as an alternative hydrogen source in transfer hydrogenation reactions provided a lower energy pathway to the full series of products for AM=Li−Cs. A further moderation in conditions was noted for the thermal decomposition of the (silyl)(hydrido)aluminates, AM[Al(NON Dipp )(H)(SiH 2 Ph)]. Probing the reaction of Cs[Al(NON Dipp )] with 1,4‐CHD provided access to a novel inverse sandwich complex, [{Cs(Et 2 O)} 2 {Al(NON Dipp )(H)} 2 (C 6 H 6 )], containing the 1,4‐dialuminated [C 6 H 6 ] 2− dianion and representing the first time that an intermediate in the commonly utilized oxidation process of 1,4‐CHD to benzene has been trapped. The synthetic utility of the newly installed Al−H bonds has been demonstrated by their ability to reduce CO 2 under mild conditions to form the bis‐formate AM[Al(NON Dipp )(O 2 CH) 2 ] compounds, which exhibit a diverse series of eyecatching bimetallacyclic structures.