Multiple d-d bonds between early transition metals in TM2Lin (TM = Sc, Ti) superatomic molecule clusters.

Abstract

The synthesis and application of compounds with Cr-Cr and V-V d-d quintuple bonds (σ, 2π, 2δ) have led to new thinking about whether d-d multiple bonds also exist between early transition metals such as Sc-Sc and Ti-Ti. In this study, by extensive unbiased global search at the density functional theory level, the low-energy structures of 26e and 30e TM2Lin clusters were obtained. Based on the super valence bond (SVB) theory, the prolate double-core structure of TM2Lin clusters was regarded as a superatomic molecule, of which each half was regarded as an open-shell superatom, and the electronic shell-closure was realized by forming multiple bonds between superatoms. Then, the quintuple super bonds (2δ, 2π, σ) of the Li18Ti2, Li20Sc2, [Li17V2]+, [Li17Ti2]- clusters and the triple super bonds (2π, σ) of the Li24Sc2 and Li24Y2 clusters were confirmed via chemical-bonding analysis. This way of forming multiple bonds between early transition metals through superatomic bonding has promoted the experimental synthesis and application of early transition metal multiple bond compounds.