Mass spectrometric and theoretical studies on the decarboxylation of the anionic lithium complexes of the doubly deprotonated dicarboxylic acids

On the basis of the tandem mass spectrometry (MS/MS) technique and density functional theory (DFT) calculations, we have studied the decarboxylation reactions of several anionic lithium complexes of the doubly deprotonated dicarboxylic acids, which include succinic acid, l-malic acid, l-mercaptosuccinic acid, l-aspartic acid and oxaloacetic acid, etc. Tandem mass spectrometry experiments indicate that the decarboxylation reactions of these complexes in the gas phase can all take place. DFT calculations show that the α-substituted groups in the dicarboxylic acids, such as OH, NH2 and SH can advance the decarboxylation of the corresponding anionic lithium complexes. Meanwhile, the decarboxylation generally happens at the carboxylate group that is away from the substituent. This opinion is also supported by the bond angle analyses of the carboxylate groups.

► Using MS/MS technique and DFT to study the decarboxylation of several anionic lithium complexes.
► The α-substituted groups in the dicarboxylic acids can advance the decarboxylation.
► The decarboxylation generally happens to the carboxylate group away from the substituent.