Two atoms at once: ligand skeleton expansion by a -CN- unit via nitrile insertion into the pyridinium amidate backbone of platinum complexes.

We demonstrate the selective and direct platinum-mediated insertion of a nitrile fragment into the C-N bond of a pyridinium amidate scaffold. This reactivity expands the ligand skeleton through the insertion of two atoms at once. Isotope labelling indicates N-Cpyridinium bond cleavage in the ligand, and time-dependent monitoring suggests the formation of multiple intermediates en route to the final nitrile-inserted complex.