Elucidating the Electronic Structure of the Ligated Cuboctahedral Palladium Cluster [Pd13(μ4-C7H7)6]2+

Jianyu Wei (1) , Samia Kahlal (1) , Jean-François Halet (1) , Jean-Yves Saillard (1)

1 ISCR - Institut des Sciences Chimiques de Rennes

The electronic structure of the recently reported cuboctahedral [Pd13(μ4-Tr)6]2+ (Tr = C7H7) cluster is analyzed using DFT calculations. Results indicate that the bonding in this cluster can be described from the formal starting point of a [Pd13]2− core interacting with a partly reduced [Tr6]4+ ligand shell. The orbital interactions between the two fragments are strong, owing in particular to the very strong accepting ability of the surrounding ligands. The (moderate) Pd–Pd bonding character is in part due to the occupation of the strongly bonding in-phase combination of the 5s(Pd) orbitals (the 1S jellium level) and for another part from through-bond interactions.

Keywords: Cuboctahedron; DFT; Electron counting; Palladium clusters; Superatoms

Domains: Chemical Sciences

Jianyu Wei, Samia Kahlal, Jean-François Halet, Jean-Yves Saillard. Elucidating the Electronic Structure of the Ligated Cuboctahedral Palladium Cluster [Pd13(μ4-C7H7)6]2+. Journal of Cluster Science, 2019, 30 (5), pp.1227-1233. ⟨10.1007/s10876-019-01616-6⟩. ⟨hal-02181829⟩