Anions featuring an aluminium-silicon core with alumanyl silanide and aluminata-silene characteristics

Molecular species containing multiple bonds to aluminium have long been challenging synthetic targets. Despite recent landmark discoveries in this area, heterodinuclear Al-E multiple bonds (where E is a group-14 element) have remained rare and limited to highly polarized π-interactions (Al=E ↔ ⁺Al-E^-). Here we report the isolation of three alumanyl silanide anions that feature an Al-Si core stabilized by bulky substituents and a Si-Na interaction. Single-crystal X-ray diffraction studies, spectroscopic analysis and density functional theory calculations show that the Al-Si interaction possesses partial double bond character. Preliminary reactivity studies support this description of the compounds through two resonance structures: one that displays a predominant nucleophilic character of the sodium-coordinated silicon centre in the Al-Si core, as shown by silanide-like reactivity towards halosilane electrophiles and the CH-insertion of phenylacetylene. Moreover, we report an alumanyl silanide with a sequestered sodium cation. Cleavage of the Si-Na bond by [2.2.2]cryptand increases the double bond character of the Al-Si core to produce an anion with high aluminata-silene (^-Al=Si) character.