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-NSi^t 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.