A MINDO/3 study on the monoelectronic reduction of carbon monoxide: The acetylenediolate dianion as the first member and as the common precursor of all the cyclic oxocarbon dianions

Abstract

The formation of acetylenediolate (C 2O 2 2−) in the monoelectronic reduction of carbon monoxide has been studied by the MINDO/3 method. According to the present results, carbon monoxide is first reduced to its radical anion, which adds to a second molecule of carbon monoxide to form the ethylenedione radical anion, which is then further reduced to C 2O 2 2−. The partial oxidation of acetylenediolate to oxalate dianion, as well as the electrochemical synthesis of squarate dianion from carbon monoxide, are interpreted in terms of the proposed mechanism.