Acylphosphines are an attractive subclass of phosphine ligands with specific reactivity and ligating properties. This study describes the synthesis of a ferrocene-based acylphosphine, FcC(O)PPh2 (1, Fc = ferrocenyl), the corresponding phosphine chalcogenides FcC(O)P(E)Ph2 (E = O, S and Se), and palladium(ii) complexes resulting from the orthometallation of 1, viz. [Pd(μ-X)(1- H)]2 (2-X, where X = Cl, Br and I), which in turn serve as a convenient entry point to a range of monopalladium complexes. Thus, the cleavage of 2-X with phosphines, 4-(dimethylamino)pyridine and in situ-generated 1,3-dimesitylimidazolin-2-ylidene (L) provided complexes [PdX(L)(1- H)] (3-5), which are typically obtained as single isomers by crystallisation but undergo spontaneous isomerisation in solution leading to equilibrium mixtures of cis and trans isomers. Upon treatment with sodium acetylacetonate (Na(acac)), 2-Cl was transformed into [Pd(acac)(1- H)] (6), which reacted with (diphenylphosphino)acetic acid under proton transfer to give [Pd(Ph2PCH2CO2-κ2O,P)(1- H)] (7), while the reaction with allylating agents produced the π-allyl complex [Pd(η3-C3H5)(1- H)] (9). Compound [PdCl(PMe3)(1- H)] was further used to prepare a series of diorganopalladium complexes [Pd(R)(PMe3)(1- H)] (8; R = Me, 4-C6H4Me, 4-C6H4CF3, CH[double bond, length as m-dash]CHC6H4Me-4 and C[triple bond, length as m-dash]CC6H4Me-4). All compounds were structurally characterised using spectroscopic methods and, in most cases, also by X-ray diffraction analysis. The structural data indicated the rigidity of the Pd(1- H)+ fragment and revealed variations in the Pd-donor distances dictated by an interplay between the trans influence and steric demands of the ligands surrounding Pd(ii). Moreover, some compounds were studied by DFT to rationalise their isomerisation equilibria and electrochemical properties, which were examined by cyclic voltammetry.