Lanthanides with Unusually Low Oxidation States in the PrB3- and PrB4- Boride Clusters.

Lanthanide elements typically exhibit a +III oxidation state (OS) in chemical compounds with a few in +IV or even +V OS. Although lanthanides with +II OS have been observed recently in organometallic compounds, +I OS is extremely rare. Using a joint photoelectron spectroscopy and quantum theoretical study, we have found two low OS lanthanides in doped boron clusters, PrB3- and PrB4-. These two clusters are shown to have planar structures, in which the Pr atom is bonded to the aromatic boron clusters via two Pr-B σ bonds. Chemical bonding and electronic structure analyses reveal that the Pr atom is in a very low OS in the two boride clusters: +II in PrB3- and +I in PrB4-. The current finding suggests that there should exist a whole class of boride complexes featuring rather low-valent lanthanides and expands the frontier of lanthanide chemistry.