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.

Infrared Photodissociation Spectroscopy of Dinuclear Vanadium-Group Metal Carbonyl Complexes: Diatomic Synergistic Activation of Carbon Monoxide

“…The preliminary structure optimization yielded considerable candidates, in which the three lowest spin states, namely the doublet, quartet and sextet of each candidate isomer were considered. To the best of our knowledge, the B3LYP functional is capable of providing accurate vibrational spectra of carbonyl complexes involving transition metals [14,16,18,19], but is much inferior to the non-hybrid functionals in terms of energy calculation and bond length prediction [52][53][54]. Therefore, the resulting low-lying candidates from the preliminary structure search were further reoptimized at the B3LYP, BLYP, PBE, and TPSS level in conjunction with the def2-TZVP basis set to obtain more accurate energetical results and structural parameters [45,50,51,[55][56][57][58].…”

“…Infrared photodissociation spectroscopy (IRPD) has proven to be a powerful tool allowing for structural identification of mass-selected charged clusters in the gas phase [10][11][12], as well as an understanding of bonding interactions between core atoms in conjunction with density functional calculations [13][14][15][16][17][18][19]. In addition, carbon monoxide (CO) acts as an ideal probe for detecting metal-ligand interactions owing to its strong infrared absorption and simple vibration pattern.…”

Gas-phase and solid-state electronic structure analysis and DFT benchmarking of HfCO

“…In general, unsaturated TM(CO) n complexes have several close-lying electronic states, which make them challenging to model accurately with computation. 14,[19][20][21][22][23] High-level multi-reference theories provide a platform for predictions of systems with many lowlying electronic states. 24,25 The gold-standard coupled cluster level of theory can also deliver predictions with higher precision relative to most computationally tractable multi-reference (MR) methods as long as the targeted states are sufficiently single-reference (SR) in nature.…”

“…13 Computational modelling is vital in understanding the chemistry of systems that are challenging to handle under laboratory conditions. [14][15][16] For example, Hf compounds are known to be highly toxic, motivating theoretical studies. 17,18 However, selection of appropriate computational tools is crucial to make accurate predictions.…”

Gas-Phase and Solid-State Electronic Structure Analysis and DFT Benchmarking of HfCO

“…In general, unsaturated TM(CO)n complexes have several close-lying electronic states, which make them challenging to model accurately with computation. 14,[19][20][21][22][23] High-level multi-reference theories provide a platform for predictions of systems with many low-lying electronic states. 24,25 The gold-standard coupled cluster level of theory can also deliver predictions with higher precision relative to most computationally tractable MR methods as long as the targeted states are sufficiently singlereference in nature.…”