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/anie.201901599

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

Journal Article · Sun Mar 03 00:00:00 EST 2019 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.201901599· OSTI ID:1524646

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

^[2]

Columbia Univ., New York, NY (United States)
Harvard Univ., Cambridge, MA (United States)
Univ. of California, Berkeley, CA (United States)
Univ. of Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

The trichromium cluster (^tbsL)Cr₃(thf) ([^tbsL]^6–=[1,3,5-C₆H₉(NC₆H₄-o-NSi^tBuMe₂)₃]^6–) exhibits steric- and solvation-controlled reactivity with organic azides to form three distinct products: reaction of (^tbsL)Cr₃(thf) with benzyl azide forms a symmetrized bridging imido complex (^tbsL)Cr₃(μ³-NBn); reaction with mesityl azide in benzene affords a terminally bound imido complex (^tbsL)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 (^tbsL)Cr₃(μ³-N). We report 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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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: National Institutes of Health (NIH); USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: GM 098395; SC0008313; NSF/CHE-1834750; AC02-06CH11357

OSTI ID:: 1524646

Alternate ID(s):: OSTI ID: 1503715

Journal Information:: Angewandte Chemie (International Edition), Vol. 58, Issue 17; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 9 works

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

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