An N-heterocyclic carbene ligand precursor bearing a π-extended phenanthridine (3,4-benzoquinoline) unit is presented. The proligand was isolated as the imidazolium salt of chloride (1•HCl), bromide (1•HBr), or hexafluorophosphate (1•HPF6) counterions. These salts can be deprotonated and the carbene installed on silver centres using Ag2O as both a base and a source of metal ion. The resulting Ag(I) complex (1)AgCl can be used in a transmetalation reaction to generate a Pd(II) coordination complex (1)Pd(CH3CN)Cl2. The characterization and photophysical properties of these complexes is presented, along with a demonstration of the utility of (1)Pd(CH3CN)Cl2 in mediating a catalytic C-N cross-coupling reaction for the preparation of the pharmaceutical Piribedil.