Expanded Inverse-Sandwich Complexes of Lanthanum Borides: La₂B₁₀^- and La₂B₁₁

Inverse-sandwich structures have been observed recently for dilanthanide boride clusters, in which two Ln atoms sandwich a monocyclic B ring for x = 7-9. An interesting question is if larger B rings are possible to form such inverse-sandwich clusters. Here we address this question by investigating La₂B₁₀^- and La₂B₁₁^- using photoelectron spectroscopy and ab initio quantum chemical calculations. Photoelectron spectra of La₂B₁₀^- and La₂B₁₁^- show complicated, but well-resolved, spectral features that are used to compare with theoretical calculations. We have found that global minimum structures of the two clusters are based on the octa-boron ring. The global minimum of La₂B₁₀^- consists of two chiral enantiomers with C₁ symmetry, which can be viewed as adding a B₂ unit off-plane to the B₈ ring, whereas that of La₂B₁₁^- can be viewed as adding a B₃ unit in-plane to the B₈ ring in a second coordination shell. Chemical bonding analyses reveal localized B-B bonds on the edge of the clusters and delocalized bonds in the expanded boron frameworks. The interactions between the La atoms and the boron frameworks include the unique (d-p)δ bonding, which was found to be the key for inverse-sandwich complexes with monocyclic boron rings. The current study confirms that the largest monocyclic boron ring to form the inverse-sandwich structures is B₉ and provide insights into the structural evolutions of larger lanthanide boride clusters.