A triptycene-based diphosphine ligand was synthesized in good yield following a new route. The corresponding Pt(II)- and Ni(0)complexes were characterized. In butadiene hydrocyanation the tript-PPh2Ni(cod) catalyst leads to exceptionally high selectivities for the linear product 3-pentenenitrile, combining high activity for both hydrocyanation and isomerization. This one-step procedure could be the key toward process intensification.