Phosphine Ligand Binding and Catalytic Activity of Group 10-14 Heterobimetallic Complexes

Heterobimetallic complexes have attracted much interest due to their broad range of structures and reactivities as well as unique catalytic abilities. Additionally, these complexes can be utilized as single-source precursors for the synthesis of binary intermetallic compounds. An example is the family of bis(pyridine-2-thiolato)dichloro-germanium and tin complexes of group 10 metals (Pd and Pt). The reactivity of these heterobimetallic complexes is highly tunable through substitution of the group 14 element and the neutral ligand bound to the transition metal. Here, we study the binding energies of three different phosphorous-based ligands, PR₃ (R = Bu, Ph, and OPh) by density functional theory and restricted Hartree-Fock methods. The PR₃ ligand-binding energies follow the trend of PBu₃ > PPh₃ > P(OPh)₃, in agreement with their sigma-bonding ability. These results are confirmed by ligand exchange experiments monitored with ³¹P NMR spectroscopy, in which a weaker binding PR₃ ligand is replaced with a stronger one. Furthermore, we demonstrate that the heterobimetallic complexes are active catalysts in the Negishi coupling reaction, where stronger binding PR₃ ligands inhibit access to an active site at the metal center. Similar strategies could be applied to other complexes to better understand their ligand-binding energetics and predict their reactivity as both precursors and catalysts.