The Reaction of Nitriles and Fe+ in the Gas Phase. A Case of Remote Functionalization

Article abstract of DOI:10.1021/ja00235a016

The gas-phase reaction of bare Fe⁺ atoms with linear alkyl nitriles generates end-on complexes (1) which, depending on geometrical constraints, specifically interact with remote C-H bonds.Based on chain length effect studies and the investigation of labeled precursors, a mechanism is suggested which accounts for the chemospecificity observed for the loss of H2 and C2H4 from RCN/Fe⁺ complexes.This mechanism does not follow the analoguos reaction of Fe⁺ with alkenes and alkynes but involves an initial C-H insertion of the remote CH bonds followed by a C-C insertion.