PARALLELS IN THE FORMATION OF TRANSITION METAL-AMIDE BONDS IN SOLUTION AND IN THE GAS PHASE: AN ION CYCLOTRON RESONANCE STUDY OF COBALT ION CHEMISTRY WITH AMINES.

Article abstract of DOI:10.1021/ja00316a021

A mechanistic study of the gas-phase ion-molecule reactions of ions of the type Co(CO)//x** plus (x equals 0-2) and CoNO(CO)//x** plus (x equals 0-3) with a number of primary, secondary, and tertiary amines is presented. Primary amines exhibit a chemistry with gaseous metal ions which parallels that observed for alkanes, rather than that observed for other polar compounds. This could be largely due to a weak Co** plus -NH//2 bond which prohibits insertion of Co** plus into the polar C-N bond. Reactions of secondary and tertiary amines were used to elucidate the mechanisms of primary amines. Reactions occur in which intermediates involving secondary and tertiary amides are preferred over those involving primary amides. This behavior parallels the observed behavior of transition-metal amides in solution.