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

Bartholomew, Amymarie K.; Juda, Cristin E.; Nessralla, Jonathon N.; Lin, Benjamin; Wang, SuYin Grass; Chen, Yu‐Sheng; Betley, Theodore A.

doi:10.1002/ange.201901599

Title: Ligand‐Based Control of Single‐Site vs. Multi‐Site Reactivity by a Trichromium Cluster

Journal Article · Wed Mar 27 00:00:00 EDT 2019 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.201901599· OSTI ID:1503720

^[1]; Juda, Cristin E. ^[2]; Nessralla, Jonathon N. ^[3]; Lin, Benjamin ^[2]; Wang, SuYin Grass ^[4]; Chen, Yu‐Sheng ^[4];

^[2]

Department of Chemistry Columbia University New York NY 10027 USA
Department of Chemistry and Chemical Biology Harvard University 12 Oxford St. Cambridge MA 02138 USA
Department of Chemistry University of California, Berkeley Berkeley CA 94720 USA
ChemMatCARS Beamline The University of Chicago Advanced Photon Source Argonne IL 60429 USA

Abstract The trichromium cluster ( ^tbs L)Cr ₃ (thf) ([ ^tbs L] ⁶⁻ =[1,3,5‐C ₆ H ₉ (NC ₆ H ₄ ‐ o ‐NSi ^t BuMe ₂ ) ₃ ] ⁶⁻ ) exhibits steric‐ and solvation‐controlled reactivity with organic azides to form three distinct products: reaction of ( ^tbs L)Cr ₃ (thf) with benzyl azide forms a symmetrized bridging imido complex ( ^tbs L)Cr ₃ ( μ ³ ‐NBn); reaction with mesityl azide in benzene affords a terminally bound imido complex ( ^tbs L)Cr ₃ ( μ ¹ ‐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)Cr ₃ ( μ ³ ‐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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Sponsoring Organization:: USDOE

OSTI ID:: 1503720

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Vol. 131 Journal Issue: 17; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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