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


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 (?3 -NBn); reaction with mesityl azide in benzene affords a terminally bound imido complex (tbs L)Cr3 (?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)Cr3 (?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.

SUBMITTER: Bartholomew AK 

PROVIDER: S-EPMC6494472 | biostudies-literature | 2019 Apr

REPOSITORIES: biostudies-literature

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

Bartholomew Amymarie K AK   Juda Cristin E CE   Nessralla Jonathon N JN   Lin Benjamin B   Wang SuYin Grass SG   Chen Yu-Sheng YS   Betley Theodore A TA  

Angewandte Chemie (International ed. in English) 20190327 17


The trichromium cluster (<sup>tbs</sup> L)Cr<sub>3</sub> (thf) ([<sup>tbs</sup> L]<sup>6-</sup> =[1,3,5-C<sub>6</sub> H<sub>9</sub> (NC<sub>6</sub> H<sub>4</sub> -o-NSi<sup>t</sup> BuMe<sub>2</sub> )<sub>3</sub> ]<sup>6-</sup> ) exhibits steric- and solvation-controlled reactivity with organic azides to form three distinct products: reaction of (<sup>tbs</sup> L)Cr<sub>3</sub> (thf) with benzyl azide forms a symmetrized bridging imido complex (<sup>tbs</sup> L)Cr<sub>3</sub> (μ<sup>3</sup> -NBn)  ...[more]

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