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

Abstract

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 PbB2O– and PbB3O2–, which are produced and characterized in a cluster beam. PbB2O– 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. PbB3O2– 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.

Investigation of Pb–B Bonding in PbB2(BO)n− (n = 0–2): Transformation from Aromatic PbB2− to Pb[B2(BO)2]−/0 Complexes with BB Triple Bonds

“…It has a Y-shaped structure (Fig. 4), similar to the recently reported C 2v PbB 3 O 2 − , 76 and can be viewed as two boronyl groups and one Pb–B unit coordinated to a central B atom. Overall, the GM structures of PbB 2 − ( 1 ), PbB 3 O − ( 2 ), and PbB 4 O 2 − ( 3 ) can be expressed as [PbB 2 (BO) n ] − ( n = 0–2), i.e.…”

“…We have studied recently two lead-doped boron oxide clusters, PbB 2 O −/2− and PbB 3 O 2 − and found a PbB triple bond in the linear PbB 2 O 2− species, a BPb multiple bond with a bond order of 2.5 in the linear PbB 2 O − , and a BPb double bond in the Y-shaped PbB 3 O 2 − . 76…”

Numerical characterization of the electronic and optical properties of plumbene/hBN heterobilayer using first-principles study

“…Structures I, II, and III have optimized interlayer distances of 3.560 Å, 3.498 Å, and 3.506 Å, respectively. These optimal interlayer distances are all fairly greater than the Pb–B bond length (2.122 Å) 31 and the Pb–N bond length (2.75 Å). 32 Therefore, Pb atoms of the plumbene layer are expected not to form covalent bonds with B and N atoms of the hBN layer.…”

Infrared Photodissociation Spectroscopy of Mass-Selected Dinuclear Transition Metal Boride Carbonyl Cluster Cations

“…Indeed, new exciting discoveries about boron-containing compounds continue to emerge. Very recently, electron-precise transition-metal–boron triple bonds were unveiled in several linear anions in the form of [MB–BO] − (M = Bi, Pb, Re, and Ir) by photoelectron spectroscopy experiments combined with theoretical calculations. − More intriguingly, Wang and co-workers demonstrated a quadruple bond between boron and rhodium in RhB­(BO) − and neutral RhB, which consists of two π bonds formed between the Rh 4 d xz /4 d yz and B 2 p x /2 p y orbitals and two σ-bonds between the Rh 4 d z 2 and B 2 s /2 p z orbitals . In addition, the transition-metal–boron single-, double-, and triple-bond complexes were trapped in excess solid neon and argon and identified through matrix isolation infrared spectroscopy and quantum chemical calculations by our group. − Zhou and co-workers reported the anionic complex BFe­(CO) 3 – with unexpected 4-fold chemical bonds between B and Fe, including one electron-sharing σ bond, two Fe-to-B dative π bonds, and a weak B-to-Fe dative σ bond .…”