Bismuth–Boron Multiple Bonding in BiB₂O⁻ and Bi₂B⁻

Abstract

Despite its electron deficiency, boron is versatile in forming multiple bonds. Transition-metal-boron double bonding is known, but boron-metal triple bonds have been elusive. Two bismuth boron cluster anions, BiB O and Bi B , containing triple and double B-Bi bonds are presented. The BiB O and Bi B clusters are produced by laser vaporization of a mixed B/Bi target and characterized by photoelectron spectroscopy and ab initio calculations. Well-resolved photoelectron spectra are obtained and interpreted with the help of ab initio calculations, which show that both species are linear. Chemical bonding analyses reveal that Bi forms triple and double bonds with boron in BiB O ([Bi≡B-B≡O] ) and Bi B ([Bi=B=Bi] ), respectively. The Bi-B double and triple bond strengths are calculated to be 3.21 and 4.70 eV, respectively. This is the first experimental observation of Bi-B double and triple bonds, opening the door to design main-group metal-boron complexes with multiple bonding.

High resolution photoelectron imaging of boron-bismuth binary clusters: Bi2Bn− (n = 2–4)

“…The Bi-B bond length in Bi 2 B 2 is very similar to the Bi= =B double bonds in Bi 2 B − . 9 There is a small change in the Bi-B and B-B bond lengths between the neutral and the anion. Both the Bi-B and B-B bond lengths in the linear Bi 2 B 2 cluster are slightly shorter than the Bi= =B and B= =B double bond lengths calculated from Pyykko's self-consistent atomic covalent radii of B and Bi.…”

“…8 Recently, we have discovered a double-bonded Bi= =B species in Bi 2 B − ([Bi= =B= =Bi] − ) and a triple-bonded Bi≡≡B species in BiB 2 O − ([Bi≡≡B-B≡≡O] − ). 9 In the current work, we report a PES and theoretical study on a series of di-bismuth boride clusters, Bi 2 B n − (n = 2-4).…”

Structural Evolution of Gold-Doped Bismuth Clusters AuBin– (n = 4–8)

“…Frequency calculations were done to verify that the isomers were true minima on the potential energy surface. The inclusion of spin−orbit (SO) effects is essential for both gold and bismuth, 30,58 and previous studies on gold or gold-doped clusters have shown that inclusion of SO effects provided quantitatively better theoretical data for comparison with experimental PES spectra. 59−61 Next, single-point energies of these candidate isomers were calculated at the SODFT level using the PBE0 functional 62 and the CRENBL (ECP) 63 basis set, as implemented in the NWCHEM 6.3 package.…”

Triple Bonds Between Iron and Heavier Group 15 Elements in AFe(CO)3− (A=As, Sb, Bi) Complexes

“…No unequivocal TM-bismuth triplebonded species has been reported experimentally so far, [9,14] although complexes with main-group-bismutht riple bonds (for example,B i ÀBt riple bond in BiB 2 O À )a re known. [15] Theoretical calculations suggest that the bismuthido complex [(N 3 N)W Bi]c ontains W Bi triple bond, and should be stable enough to be isolated. [12] While triple bonding between transition metals and the heavier Group 14 and Group 15 elements is known, it is confined to the Group 5and Group 6 early transition metals.…”