Formation and Characterization of BeFe(CO)₄⁻ Anion with Beryllium−Iron Bonding

Abstract

Heteronuclear BeFe(CO)4− anion complex is generated in the gas phase, which is detected by mass‐selected infrared photodissociation spectroscopy in the carbonyl stretching frequency region. The complex is characterized to have a Be−Fe bonded Be−Fe(CO)4− structure with C3v symmetry and all of the four carbonyl ligands bonded on the iron center. Quantum chemical studies indicate that the complex has a quite short Be−Fe bond. Besides one electron‐sharing σ bond, there are two additional, albeit weak, Be ← Fe(CO)4− dative π bonding interactions. The findings imply that metal–metal bonding between s‐block and transition metals is viable under suitable coordination environment.

Two σ- and two π-dative quadruple bonds between the s-block element and transition metal in [BeM(CO)4; M = Fe − Os]

“…On the other hand, BeFe(CO) 4 − , identified in the gas phase by mass-selected infrared photodissociation spectroscopy, shows only triple bonds, a one-electron sharing σ-bond, and two weak dative π-bonds. 28…”

“…The Fe – Be bond length (1.915 Å) in Fe – Be is shorter than those reported for BeFe(CO) 4 − (2.02 Å, 2.03 Å and 2.06 Å, respectively, at the PBE, B3LYP, and M06-2X levels), where the Fe – Be bond in the latter is reported as a triple bond. 28 The equatorial OC–M–CO bond angle gets wider as the transition metal changes from Fe to Os. The two axial CO ligands in Fe – Be (76.3°) and Ru–Be (86.5°) are tilted towards beryllium.…”

Triple bonding between beryllium and nitrogen in HNBeCO

“…Besides one electron-sharing s bond, there are two additional, albeit weak, Be'Fe(CO) 4 dative p bonding interactions. 8 Besides metal-metal multiple bonding, beryllium can also form multiple bonds with carbon and nitrogen. A compound C 6 H 3 Mes 2 Be-N(SiMe 3 ) 2 (Mes = ÀC 6 H 2 -2,4,6-Me 3 ) was structurally characterized in 1997.…”

Photoelectron velocity-map imaging spectroscopy of nickel carbide: examination of the low-lying electronic states

“…60 Previous CASSCF calculations show that the CI weight of dominant configuration is 88% for the NiC ground state, 53 suggesting that the structural and chemical bond properties based on single determinant calculations are qualitatively reasonable. 61–63 The pure BP86 functional utilizing Becke's 1988 exchange functional and Perdew's correlation functional 64,65 was proved to be practical, 66,67 and thus was employed for geometry optimization and electronic structure analysis in conjunction with the def2-TZVPP basis sets. The dispersion forces were considered based on Grimme's approach with the Becke—Johnson damping correction (D3(BJ)).…”