Carboxylic Acid Ester Adducts of Beryllium Chloride and Their Role in the Synthesis of Beryllium Nitrates

To investigate the synthetic route towards anhydrous Be(NO 3 ) 2 ( 2 ), beryllium esterates [BeCl 2 (MeOAc) 2 ] ( 4a ), [BeCl 2 (EtOAc) 2 ] ( 4b ), [BeCl 2 ( i PrOAc) 2 ] ( 4c ), [BeCl 2 (MeOForm) 2 ] ( 4d ), [BeCl 2 (EtOForm) 2 ] ( 4e ), and [BeCl 2 ( i PrOForm) 2 ] ( 4f ) were synthesized and spectroscopically characterized. Additionally, the crystal structure of [BeCl 2 (MeOAc) 2 ] ( 4a ) was determined and DFT calculations on these adducts were performed. These four‐coordinate beryllium complexes react, in contrast to BeCl 2 , readily with N 2 O 4 under the evolution of NOCl to form ester adducts of Be(NO 3 ) 2 ( 5 ), which react with excess amounts of N 2 O 4 to afford known (NO) 2 [Be(NO 3 ) 4 ] ( 1 ). However, it is not possible to completely remove the carboxylic acid esters from nitrosyl salt 1 . Therefore, the thermal decomposition leads to the formation of mixtures of beryllium nitrates 2 and 5 . Furthermore it could be shown that this mixture decomposes even at ambient temperature slowly to [Be 4 O](NO 3 ) 6 ( 3 ).