Capture of Bridging Imido and Azavinylidene Intermediates Engaged in Nitrogen Functionality Changes from Primary Azide to Nitrile on a Copper Surface

Abstract

Various nitrogen-based bridging ligands at the sites of a Cu(111) surface, including μ3-imido and μ2-azavinylidene species, have been identified by surface-sensitive spectroscopies and density functional theory (DFT) calculations. The isolated intermediates demonstrate how several metal atoms acting in concert can usher the conversion from a primary azide into a nitrile end-product. The collection of mechanistic details, the N–N2 bond scission, the sequential β-hydrogen eliminations, and the alterations of the NC unsaturation, illustrates rich information about structures and transformations of N-donor ligands.