Mimicking Base Interaction with Acidic Sites [Si–O( H )–Al] of Zeolites in Molecular Models

LiAlH 4 , LiAlMe 4 , or NaAlH 4 react with commercially available HOSi R 3 , (–OSi R 3 = –OSi t BuMe 2 , –OSiPh 3 ) to afford [Li(THF) 2 ][Al(OSi t BuMe 2 ) 4 ] ( 1 ), [Na(THF) 2 ][Al(OSi t BuMe 2 ) 4 ] ( 2 ), and [Li(THF) 4 ][Al(OSiPh 3 ) 4 ] ( 3 ). Ligand exchange reactions at the alkali metal ions in 1 and 3 with pyridine, 2,2′‐bipyrimidine, and water yielded complexes [Li(py) 2 ][Al(OSi t BuMe 2 ) 4 ] ( 4 ), [Al(OSi t BuMe 2 ) 4 Li(H 2 O)] 2 (bpym) ( 5 ), and [Li(THF)(H 2 O)][Al(OSiPh 3 ) 4 ] ( 6 ). The X‐ray crystal structures of complexes 1 , 3 , 4 , 5 , and 6 are presented. The complex [quinuclidineH][Al(OSi t BuMe 2 ) 4 ] ( 7 ), was produced via reaction of quinuclidine · hydrochloride with 2 . It features a hydrogen bonding interaction between an N–H group with a Si–O–Al unit, as proposed for the surfaces of zeolites after base treatment.