Old Acid, New Chemistry. Negative Metal Anions Generated from Alkali Metal Oxalates and Others

Abstract

A brief search in Sci Finder for oxalic acid and oxalates will reward the researcher with a staggering 129,280 hits. However, the generation of alkali metal and silver anions via collision-induced dissociation of the metal oxalate anion has not been previously been reported, though Tian and coworkers recently investigated the dissociation of lithium oxalate. The exothermic decomposition of alkali metal oxalate anion to carbon dioxide in the collision cell of a triple quadrupole mass spectrometer leaves no place for the electron to reside, resulting in a double electron-transfer reaction to produce an alkali metal anion. This reaction is facilitated by the negative electron affinity of carbon dioxide and, as such, the authors believe that metal oxalates are potentially unique in this respect. The observed dissociation reactions for collision with argon gas (1.7-1.8 × 10(-3) mbar) for oxalic acid and various alkali metal oxalates are discussed and summarized. Silver oxalate is also included to demonstrate the propensity of this system to generate transition-metal anions, as well.