Ligand-Based Control of Single-Site vs. Multi-Site Reactivity by a Trichromium Cluster
Abstract
The trichromium cluster (tbsL)Cr3(thf) ([tbsL]6–=[1,3,5-C6H9(NC6H4-o-NSitBuMe2)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.
- Authors:
-
[1];
[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)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
- Sponsoring Org.:
- National Institutes of Health (NIH); USDOE Office of Science (SC); National Science Foundation (NSF)
- OSTI Identifier:
- 1524646
- Alternate Identifier(s):
- OSTI ID: 1503715
- Grant/Contract Number:
- GM 098395; SC0008313; NSF/CHE-1834750; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Angewandte Chemie (International Edition)
- Additional Journal Information:
- Journal Name: Angewandte Chemie (International Edition); Journal Volume: 58; Journal Issue: 17; Journal ID: ISSN 1433-7851
- Publisher:
- Wiley
- Country of Publication:
- United States
- Language:
- ENGLISH
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; azides; bridging ligands; chromium complexes; cluster compounds; multi-electron reactivity
Citation Formats
Bartholomew, Amymarie K., Juda, Cristin E., Nessralla, Jonathon N., Lin, Benjamin, Wang, SuYin Grass, Chen, Yu‐Sheng, and Betley, Theodore A. Ligand-Based Control of Single-Site vs. Multi-Site Reactivity by a Trichromium Cluster. United States: N. p., 2019.
Web. doi:10.1002/anie.201901599.
Bartholomew, Amymarie K., Juda, Cristin E., Nessralla, Jonathon N., Lin, Benjamin, Wang, SuYin Grass, Chen, Yu‐Sheng, & Betley, Theodore A. Ligand-Based Control of Single-Site vs. Multi-Site Reactivity by a Trichromium Cluster. United States. https://doi.org/10.1002/anie.201901599
Bartholomew, Amymarie K., Juda, Cristin E., Nessralla, Jonathon N., Lin, Benjamin, Wang, SuYin Grass, Chen, Yu‐Sheng, and Betley, Theodore A. Sun .
"Ligand-Based Control of Single-Site vs. Multi-Site Reactivity by a Trichromium Cluster". United States. https://doi.org/10.1002/anie.201901599. https://www.osti.gov/servlets/purl/1524646.
@article{osti_1524646,
title = {Ligand-Based Control of Single-Site vs. Multi-Site Reactivity by a Trichromium Cluster},
author = {Bartholomew, Amymarie K. and Juda, Cristin E. and Nessralla, Jonathon N. and Lin, Benjamin and Wang, SuYin Grass and Chen, Yu‐Sheng and Betley, Theodore A.},
abstractNote = {The trichromium cluster (tbsL)Cr3(thf) ([tbsL]6–=[1,3,5-C6H9(NC6H4-o-NSitBuMe2)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.},
doi = {10.1002/anie.201901599},
journal = {Angewandte Chemie (International Edition)},
number = 17,
volume = 58,
place = {United States},
year = {Sun Mar 03 00:00:00 EST 2019},
month = {Sun Mar 03 00:00:00 EST 2019}
}
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