The reaction of Pd(OAc)2 with polyfunctional iminophosphoranes Ph3PNCH2CO2Me (1a), Ph3PNCH2C(O)NMe2 (1b), Ph3PNCH2CH2SMe (1c) and Ph3PNCH2-2-NC5H4 (1d), gives the orthopalladated dinuclear complex [Pd(µ-Cl){C6H4(PPh2NCH2CO2Me-κ-C,N)-2}]2 (2a) and the mononuclear derivatives [PdCl{C6H4(PPh2NCH2CONMe2-κ-C,N,O)-2}] (2b), [PdCl{C6H4(PPh2NCH2CH2SMe-κ-C,N,S)-2}] (2c) and [PdCl{C6H4(PPh2NCH2-2-NC5H4-κ-C,N,N)-2}] (2d). The reaction implies the activation of a C–H bond in a phenyl ring of the phosphonium group, this fact being worthy of note due to the strongly deactivating nature of the phosphonium unit. The palladacycle containing the metallated carbon atom is remarkably stable toward the coordination of incoming ligands, while that formed by the iminic N atom and another heteroatom (O, 2a and 2b; S, 2c; N, 2d) is less stable and the resulting complexes can be considered as hemilabile. The X-ray crystal structures of the cyclopalladated [Pd(µ-Cl){C6H4(PPh2NCH2CO2Me-κ-C,N)-2}]2 (2a), [PdCl{C6H4(PPh2NCH2–2-NC5H4-κ-C,N,N)-2}] (2d), [Pd{C6H4(PPh2NCH2CONMe2-κ-C,N,O)-2}(NCMe)](ClO4) (3b) and [Pd{C6H4(PPh2NCH2CONMe2-κ-C,N,O)-2}(py)](ClO4) (7b), and the coordination compound cis-[Pd(Cl)2(Ph3PNCH2CH2SMe-κ-N,S)] (8) are also reported.