Newly prepared phosphinoferrocene guanidines coordinate Pd(ii) as donor-unsymmetric, P,N-chelating ligands or in κ3P,N,Fe-mode with Fe–Pd dative interactions.
amidine Ph2PfcN=CHNMe2 (fc=ferrocene-1,1′-diyl) was prepared as a new hybrid, ferrocene P,N-ligand. In complexes with the light platinum metals, the compound readily coordinated as a P-monodentate ligand. However, upon halogen removal, the phosphane complexes converted into P,N-chelates, wherein both functional moieties at the ferrocene unit were involved in coordination.