Preparation and Ground-state Electronic Structure of Heterobimetallic Ln-PtIV-alkyl complexes

This article focuses on the synthesis of heterobimetallic complexes of lanthanide and platinum. It describes the synthesis of the Cp*Yb(bipym)PtMe2 complex and its characterization, followed by its reactivity with oxidants, giving access to various Pt +IV compounds of trismethyl (PtMe3) and tetramethyl (PtMe4) fragments. Characterization of the electronic properties of the complexes by magnetic measurements demonstrated that the tetramethyl complex possesses a singlet ground state. The trismethyl fragments, on the other hand, have a ground state that evolves as a function of the ligand saturating the coordination sphere: singlet for triflate and pyridine and triplet for iodine, demonstrating the capacity for simple tuning of the electronic structure of these complexes. While the addition of B(C6F5)3 to the platinum +II bis methyl complex leads to FLP-like reactivity triggering THF opening, reactivity with [Ph3C]+[BPh4]- leads to oxidation of the bipym ligand. Furthermore, the light reactivity of the tetramethyl complex indicated the possible transfer of a methyl group, leading to the functionalization of the bridging bipym ligand.