Introducing Transition-Metal-Anchored Base-Stabilized Borylenes: A Potential Platform for the Activation of CO 2 and Other Heteroallenes

Abstract

Computational investigations were performed using density functional theory on hitherto unknown base-stabilized metalloborylenes in order to explore how the substitution of the −N(SiMe3)2 group by an isolobal metal fragment Fe(CO)2Cp* altered the ligand properties and to investigate their possibility toward the capture of greenhouse gases like CO2 and N2O as well as an industrially relevant yet toxic compound, methyl isocyanate (CH3NCO). The most probable pathways for the reaction of the heteroallenes with the proposed systems were thoroughly studied, demonstrating cooperativity between the boron center, Lewis base (carbene/silylene), and metal fragment of the base-stabilized metalloborylenes. The computed reaction free energies and barrier heights indicate the potential of the proposed systems in the activation of heteroallenes. These metalloborylenes were also predicted to be capable of generating either base-free or base-stabilized metal–oxoboryl complexes.