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Despite its electron deficiency, boron can form multiple bonds with a variety of elements. However, multiple bonds between boron and main-group metal elements are relatively rare. Here we report the observation of boron-lead multiple bonds in PbB 2 O –  and PbB 3 O 2  – , which are produced and characterized in a cluster beam. PbB 2 O –  is found to have an open-shell linear structure, in which the bond order of B☱Pb is 2.5, while the closed-shell [Pb≡B–B≡O] 2–  contains a B≡Pb triple bond. PbB 3 O 2  –  is shown to have a Y-shaped structure with a terminal B = Pb double bond coordinated by two boronyl ligands. Comparison between [Pb≡B–B≡O] 2– /[Pb=B(B≡O) 2 ] –  and the isoelectronic [Pb≡B–C≡O] – /[Pb=B(C≡O) 2 ] +  carbonyl counterparts further reveals transition-metal-like behaviors for the central B atoms. Additional theoretical studies show that Ge and Sn can form similar boron species as Pb, suggesting the possibilities to synthesize new compounds containing multiple boron bonds with heavy group-14 elements.

Boron-lead multiple bonds in the PbB2O– and PbB3O2– clusters