Chromium(III) complexes of chelating diphosphines, with PNP or PCNCP backbones, are excellent catalysts for ethylene tetra- and/or trimerisations. A missing link within this ligand series are unsymmetric chelating diphosphines based on a PCNP scaffold. New bidentate PCNP ligands of the type Ph₂PCH₂N(R)PPh₂ (R = 1-naphthyl or 5-quinoline groups, 2a–d) have been synthesised and shown to be extremely effective ligands for ethylene tri-/tetramerisations. Three representative tetracarbonyl Cr⁰ complexes bearing a single PN(R)P (5), PCN(R)P (6), or PCN(R)CP (7) diphosphine (R = 1-naphthyl) have been prepared from Cr(CO)₄(η⁴-nbd) (nbd = norbornadiene). Furthermore we report a single crystal X-ray diffraction study of these compounds and discuss their structural parameters.