Carbene-Like Reactivity in an Iron Azametallacyclobutene Complex: Insights from Electronic Structure.

Herein we describe our investigation into the electronic structure of the first isolated monometallic iron azametallacyclobutene complex. Computational analysis through density functional theory calculations reveals electron delocalization throughout the four atoms of the ring system, in line with experimental observations and supporting the classification of this complex as a conjugated metallacycle. The results of this study also point to significant contribution from an imine-substituted iron carbene resonance structure to the overall bonding picture for the azametallacyclobutene. Accordingly, this complex participates in carbene-like reactivity in the presence of an isocyanide substrate to generate a ketenimine product. The related reaction with carbon monoxide leads to the isolation of a five-membered metallacycle that is analogous to the proposed intermediate in ketenimine formation, and confirms the α-carbon as the site of reactivity.