Formation and Characterization of a BeOBeC Multiple Radical Featuring a Quartet Carbyne Moiety

The reactions of laser‐ablated beryllium atoms with dinitrogen and carbon monoxide mixtures form the end‐on bonded NNBeCO and side‐on bonded (η2‐N2)BeCO isomers in solid argon, which are predicted by quantum chemical calculations to be almost isoenergetic. The end‐on bonded complex has a triplet ground state while the side‐on bonded isomer has a singlet electronic ground state. The complexes rearrange to the energetically lowest lying NBeNCO isomer upon visible light excitation, which is characterized to be an isocyanate complex of a nitrene derivative with a triplet electronic ground state. A bonding analysis using a charge‐ and energy decomposition procedure reveals that the electronic reference state of Be in the NNBeCO isomers has an 2s02p2 excited configuration and that the metal‐ligand bonds can be described in terms of N2→Be←CO σ donation and concomitant N2←Be→CO π backdonation. The results demonstrate that the activation of N2 with the N−N bond being completely cleaved can be achieved via coupling with carbon monoxide mediated by a main group atom.

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Beryllium Atom Mediated Dinitrogen Activation via Coupling with Carbon Monoxide

Deng

Pan

Wang

et al. 2020

Angewandte Chemie

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Revisiting the Intriguing Electronic Features of the BeOBeC Carbyne and Some Isomers: A Quantum‐Chemical Assessment

Geng

Weiske

et al. 2020

Angewandte Chemie

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Extensive high‐level quantum‐chemical calculations reveal that the rod‐shaped molecule BeOBeC, which was recently generated in matrix experiments, exists in two nearly isoenergetic states, the 5Σ quintet (56) and the 3Σ triplet (36). Their IR features are hardly distinguishable at finite temperature. The major difference concerns the mode of spin coupling between the terminal beryllium and carbon atoms. Further, the ground‐state potential‐energy surface of the [2Be,C,O] system at 4 K is presented and differences between the photochemical and thermal behaviors are highlighted. Finally, a previously not considered, so far unknown C2v‐symmetric rhombus‐like four‐membered ring 3[Be(O)(C)Be] (35) is predicted to represent the global minimum on the potential‐energy surface.

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A Homoleptic Beryllium Carbonyl Complex with an End‐On and Side‐On Bridging Carbonyl Ligand

et al. 2020

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Homoleptic dinuclear beryllium carbonyl cation complexes have been produced and characterized in the gas phase. Infrared photodissociation spectroscopic and theoretical results confirm that Be 2 (CO) 5 + is a coordination saturated complex that can be assigned to a mixture of two almost isoenergetic structural isomers. Besides a beryllium-beryllium single-bonded (OC) 2 Be-Be(CO) 3 + isomer, another structure involving an unusual end-on and side-on bridging carbonyl ligand with very low carbonyl stretching frequency is identified. Carbonmonoxidecanbindtomanytransition-metalcentersin forming diverse transition-metal carbonyl complexes, which are not only of close relevance to many industrial processes in synthesis [1] and catalysis, [2] but also served as prototypical models in understanding the metal-ligand and metal-metal bonding. [3] The carbon monoxide ligands engage in a range of bonding modes in the transition metal carbonyl complexes. [4] Besides the ubiquitous terminal end-on type, the symmetrical and unsymmetrical end-on bridging, [5] the sideon bridging [6,7] as well as the linear M-C-O-M bridging [8] coordination modes are also known in bi-and multinuclear transition metal carbonyl complexes.Compared to the countless transition-metal carbonyl complexes, only very few stable main-group metal carbonyl complexes have been synthesized and crystallographically characterized owing to the lack of accessible valence d orbitals for bonding with carbon monoxide. [9][10][11] Most of homoleptic carbonyl complexes of main group elements are not stable at ambient conditions, and they can usually only be observed in low-temperature matrices [12][13][14][15][16] or in the gas phase. [17][18][19] In these main-group element carbonyl complexes, the carbon monoxide ligand binds predominantly in terminal end-on mode. The other coordination modes that are quite common in transition-metal carbonyl complexes are rarely observed in the main-group element carbonyl complexes. Only very few dinuclear Group 13 metal carbonyl complexes were reported to involve the end-on bridging carbonyl ligands, [20] and a high-lying BeCOBe species has been characterized to involve a linear bridging CO unit. [21]

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Formation and Characterization of a BeOBeC Multiple Radical Featuring a Quartet Carbyne Moiety

Cited by 9 publications

References 77 publications

Beryllium Atom Mediated Dinitrogen Activation via Coupling with Carbon Monoxide

Beryllium Atom Mediated Dinitrogen Activation via Coupling with Carbon Monoxide

Revisiting the Intriguing Electronic Features of the BeOBeC Carbyne and Some Isomers: A Quantum‐Chemical Assessment

A Homoleptic Beryllium Carbonyl Complex with an End‐On and Side‐On Bridging Carbonyl Ligand

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