Preparation and Ground-State Electronic Structure of Heterobimetallic Yb–PtIV-Alkyl Complexes

• Published in: Inorganic chemistry 2024-10, Vol.63 (42), p.19728-19737
• Main Authors: Tricoire, Maxime, Danoun, Grégory, Nocton, Grégory
• Format: Article
• Language: English
• ISSN: 0020-1669; 1520-510X; 1520-510X
• DOI: 10.1021/acs.inorgchem.4c02921

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.