The synthesis, as well as the structural and spectroscopic characterization of the palladium(II) complex [Pd{(Ph 2 P) 2 N(CH 2 ) 3 Si(OCH 3 ) 3 -κ P,P ′}I 2 ], bearing the bis(phosphino)amine ligand (P,P) = (Ph 2 P) 2 N(CH 2 ) 3 Si(OCH 3 ) 3 , is described. X-ray crystallography studies revealed a square planar PdP 2 I 2 coordination sphere, the structural features of which are compared with those of analogous nickel(II), palladium(II) and platinum(II) complexes. The three complexes [Pd(P,P)X 2 ], X = Cl, Br, I, along with [Pd{(Ph 2 P) 2 N(( S )-CHPhMe)-κ P,P ′}Cl 2 ] and [Pd{(Ph 2 PSe)(Ph 2 P)N(( S )-CHMePh)-κ P,Se }Cl 2 ], were tested as catalysts in homogeneous hydroalkoxycarbonylation reactions. The hydroalkoxycarbonylation of styrene proved to be perfectly regioselective towards the branched ester. Complex [Pd(P,P)Cl 2 ] showed remarkably higher activity compared with that of [Pd(P,P)X 2 ], X = Br, I. Furthermore, complex [Pd(P,P)I 2 ] was studied as a homogeneous catalyst precursor in the Suzuki–Miyaura C−C coupling reaction between aryl bromides and phenylboronic acid. Complex [Pd(P,P)I 2 ] was immobilized onto STx–1 montmorillonite clay and the catalytic reactivity of the heterogenized catalyst was also investigated in both hydroalkoxycarbonylation and Suzuki–Miyaura reactions. [ABSTRACT FROM AUTHOR]