Preparation and Ground-State Electronic Structure of Heterobimetallic Yb–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: a singlet for triflate and pyridine and a 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 functionalization of the bridging bipym ligand.