Ligand-Based Control of Single-Site vs. Multi-Site Reactivity by a Trichromium Cluster.

The trichromium cluster (tbs L)Cr3 (thf) ([tbs L]6- =[1,3,5-C6 H9 (NC6 H4 -o-NSit BuMe2 )3 ]6- ) exhibits steric- and solvation-controlled reactivity with organic azides to form three distinct products: reaction of (tbs L)Cr3 (thf) with benzyl azide forms a symmetrized bridging imido complex (tbs L)Cr3 (μ3 -NBn); reaction with mesityl azide in benzene affords a terminally bound imido complex (tbs L)Cr3 (μ1 -NMes); whereas the reaction with mesityl azide in THF leads to terminal N-atom excision from the azide to yield the nitride complex (tbs L)Cr3 (μ3 -N). The reactivity of this complex demonstrates the ability of the cluster-templating ligand to produce a well-defined polynuclear transition metal cluster that can access distinct single-site and cooperative reactivity controlled by either substrate steric demands or reaction media.