The iminophosphine 2-(2-Ph₂P)C₆H₄NCHC₆H₄OH (P-N-OH) reacts with [Pd(μ-Cl)(η³-C₃H₅)]₂ yielding [PdCl(P-N-O)] and propene. In the presence of NEt₃, the reaction of P-N-OH with [Pd(μ-Cl)(η³-1-R¹,3-R²C₃H₃)]₂ (R¹ = R² = H, Ph; R¹ = H, R² = Ph) affords the η¹-allyl derivatives [Pd(η¹-1-R¹,3-R²C₃H₃)](P-N-O)] (R¹ = R² = H: 1; R¹ = H, R² = Ph: 2; R¹ = R² = Ph: 3). In solution, the complexes 1 and 3 undergo a slow dynamic process which interconverts the bonding site of the allyl ligand. The X-ray structural analysis of 1 indicates a square-planar coordination geometry around the palladium centre with a P,N,O,-tridentate ligand and a σ bonded allyl group. The complexes [PdR(P-N-O)] (R = C₆H₄Me-4, CCPh) react slowly with p-bromoanisole in the presence of p-tolylboronic acid to give [PdBr(P-N-O)] and the coupling product RC₆H₄OMe-4. The latter reactions also proceed at a low rate under catalytic conditions. The coupling of allyl bromide with p-tolylboronic acid is catalyzed by [PdCl(P-N-O)]/K₂CO₃ to give 4-allyltoluene.