Beryllium atoms react with dinitrogen and carbon monoxide mixtures to form the end‐on bonded NNBeCO and side‐on bonded (η2‐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 major group atom.
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.
Wiley: Angewandte Chemie International Edition: Table of Contents
Authors: Guohai Deng, Sudip Pan, Guanjun Wang, Lili Zhao, Mingfei Zhou, Gernot Frenking