Gas-Phase Reactions of Groups 8-10 Transition-Metal Ions with Nitroalkanes

Article abstract of DOI:10.1021/ja00292a020

Fe(1+), Co(1+), and Ni(1+) exhibit a rich chemistry in their reactions with nitroalkanes.Oxidative addition of the metal ion into the C-N bond dominates the chemistry of Ni(1+).Fe(1+), however, preferentially attacks the stronger N-O and C-C bonds, while Co(1+) reacts in a manner intermediate to Fe(1+) and Ni(1+).An unusual reaction pathway for all three metals is an apparent nitro-to-nitrite isomerisation.In addition, following C-C insertion, radical loss processes dominate over processes involving β-hydrogen abstraction.The structures of the reaction products were probed by collision-induced dissociation and secondary ion-molecule reactions with the nitroalkane.The effect of total pressure on these reactions was also studied.Evidence is presented for a long-lived (>1 ms) reaction intermediate of C-N insertion which undergoes stabilising collision in the presence of a relatively high pressure (ca. 1e-5 torr) of an inert gas.