Amymarie K Bartholomew1, Cristin E Juda2, Jonathon N Nessralla3, Benjamin Lin2, SuYin Grass Wang4, Yu-Sheng Chen4, Theodore A Betley2. 1. Department of Chemistry, Columbia University, New York, NY, 10027, USA. 2. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St., Cambridge, MA, 02138, USA. 3. Department of Chemistry, University of California, Berkeley, Berkeley, CA, 94720, USA. 4. ChemMatCARS Beamline, The University of Chicago, Advanced Photon Source, Argonne, IL, 60429, USA.
Abstract
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.
The trichromium cluster (n class="Chemical">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.
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