Controlled Expansion of a Strong‐Field Iron Nitride Cluster: Multi‐Site Ligand Substitution as a Strategy for Activating Interstitial Nitride Nucleophilicity

Abstract

Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces.Inthe case of the m 4 -nitrido cluster [Fe 4 (m 4 -N)(CO) 12 ] À ,t his analogy is limited owingtothe electron-withdrawing effect of carbonyl ligands on the iron nitride core.Described here is the synthesis and reactivity of [Fe 4 (m 4 -N)(CO) 8 (CNAr Mes2 ) 4 ] À ,a ne lectronrich analogue of [Fe 4 (m 4 -N)(CO) 12 ] À ,w here the interstitial nitride displays significant nucleophilicity.T his characteristic enables rational expansion with main-group and transitionmetal centers to yield unsaturated sites.T he resulting clusters displays urface-like reactivity through coordination-spheredependent atom rearrangement and metal-metal cooperativity.Supportinginformation and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.