Covalent Bonding Between Be⁺and CO₂in BeOCO⁺with a Surprisingly High Antisymmetric OCO Stretching Vibration

Abstract

The cationic complex BeOCO+ is produced in a solid neon matrix. Infrared absorption spectroscopic study shows that it has a very high antisymmetric OCO stretching vibration of 2418.9 cm–1, which is about 71 cm–1 blue-shifted from that of free CO2. The quantum chemical calculations are in very good agreement with the experimental observation. Depending on the theoretical method, a linear or quasi-linear structure is predicted for the cation. The analysis of the electronic structure shows that the bonding of Be+ to one oxygen atom induces very little charge migration between the two moieties, but it causes a significant change in the σ-charge distribution that strengthens the terminal C–O bond, leading to the observed blue shift. The bonding analysis reveals that the Be+ ← OCO donation results in strong binding due to the interference of the wave function and a charge polarization within the CO2 fragment and hybridization to Be+ but only negligible charge donation.

CO bonding in hexa‐ and pentacoordinate carboxy‐neuroglobin: A quantum mechanics/molecular mechanics and local vibrational mode study

“…As a secondary effect, the CO bond can further be weakened if the O atom gets involved in hydrogen bonding interactions, the opposite occurs if the C atom interacts with σ acceptors. 64 Comprehensive computational studies on transition metal carbonyl complexes, for example, performed by Frenking and co-workers [65][66][67][68][69][70] and other groups [71][72][73][74][75][76][77] have applied the DC model to explore the stabilizing role of CO ligands for both mono and poly-nuclear metal-carbonyl complexes. Some limitation of the DC and other Lewis type bonding model were recently pointed out.…”

Infrared spectroscopy of Be(CO2)4+in the gas phase: electron transfer and C–C coupling of CO2

“…This complex has been observed in solid neon matrix with an antisymmetric CO 2 stretching vibration of 2418.9 cm −1 , blue-shifted by 71 cm −1 from that of free CO 2 . 36 This end-on coordinated structure was predicted to be 6.0 kcal mol −1 lower in energy than the η 2 -O, O coordinated isomer with C 2v symmetry (Fig. S3, ESI†).…”

“…Recent investigation on the BeOCO + cation complex indicates that the metal–ligand bonding involves significant covalent character. 36 In order to understand the nature of the metal–ligand bonding in the Be(CO 2 ) 4 + complex, the EDA-NOCV method is used to analyze the bonding situation in isomers 1A and 1B . According to the aforementioned bonding analysis, we use the fragments [Be(CO 2 ) 2 2+ ] and [C 2 O 4 − ] for 1A , [Be(CO 2 ) 3 2+ ] and bent [CO 2 − ] for 1B as interacting species.…”

“…27 Recent investigation on the BeOCO + cation complex indicates that the metal-ligand bonding involves significant covalent character. 36 In order to understand the nature of the metal-ligand bonding in the Be(CO 2 ) 4 + complex, the EDA- ]. In isomer 1B, there are also three major components that contribute to the covalent interaction, which involve the donation of the highestlying singly or doubly occupied molecular orbitals of […”

“…[24][25][26] Recent investigation on the end-on Z 1 -O coordinated [BeOCO] + complex in solid neon matrix indicates that the bonding between the metal cation and CO 2 exhibits significant covalent character due to the interference of the wave function. 36 Here we report the generation and infrared spectroscopic characterization of the larger Be(CO 2 ) n + complexes in the gas phase, revealing the formation of electron transfer and C-C coupled species.…”