Beryllium Atom Mediated Dinitrogen Activation via Coupling with Carbon Monoxide. Issue 41 (13th August 2020)

• Record Type: Journal Article
• Authors: Deng, Guohai; Pan, Sudip; Wang, Guanjun; Zhao, Lili; Zhou, Mingfei; Frenking, Gernot
• Is Part Of: Angewandte Chemie international edition. Volume 59:Issue 41(2020)
• Page Start: 18201
• Page End: 18207
• Publication Date: 2020-08-13
• Subjects: beryllium -- bonding analysis -- dinitrogen activation -- infrared photodissociation spectroscopy -- matrix isolation; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.202007241
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: The reactions of laser‐ablated beryllium atoms with dinitrogen and carbon monoxide mixtures form the end‐on bonded NNBeCO and side‐on bonded (η 2 ‐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 2s 0 2p 2 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. Abstract : Beryllium atoms react with dinitrogen and carbon monoxide mixtures to form the end‐on bonded NNBeCO and side‐on bonded (η 2 ‐N2 )BeCO complexes, both of which isomerize to the more stable NBeNCO isomer, showing that the activation of N2 with fully cleaved N−N bond can be achieved by coupling with carbon monoxide via a main group atom.