The Chemistry of First-Row Transition-Metal Ions with Primary Amines in the Gas Phase: Correlations of Reactivity with Electronic Structure

Article abstract of DOI:10.1021/ja00337a013

In the past several years, an extensive body of literature has appeared in the area of gas-phase organometallic ion/molecule reactions.Most of the observed reactions can be explained by assuming that the first step of the interaction is a metal ion insertion into a bond of the organic molecule.Presented here are reactions of first-row transition-metal ions with a primary amine.They parallel the literature in that, for other types of organic molecules as well, Fe⁺ typically inserts into many types of bonds, Ni⁺ is very selective in this regard, Co⁺ is intermediate between Fe⁺ and Ni⁺, and Mn⁺ is frequently unreactive.An explanation of the reactivity trends of the first-row transition-metal ions is suggested, based on a consideration of the thermodynamics of the metal insertion process.The explanation uses the concept of promotion energy, the energy required to achieve a metal ion configuration conducive to the formation of two ?-bonds.Available data on excited states of these metal ions leads to an ordering in terms of these promotion energies, which appear to correlate with reactivity in terms of ability to insert into various bonds in organic molecules.