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Ligand‐Based Control of Single‐Site vs. Multi‐Site Reactivity by a Trichromium Cluster
Author(s) -
Bartholomew Amymarie K.,
Juda Cristin E.,
Nessralla Jonathon N.,
Lin Benjamin,
Wang SuYin Grass,
Chen YuSheng,
Betley Theodore A.
Publication year - 2019
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201901599
Subject(s) - reactivity (psychology) , chemistry , azide , steric effects , ligand (biochemistry) , cluster (spacecraft) , stereochemistry , benzene , medicinal chemistry , photochemistry , organic chemistry , receptor , medicine , biochemistry , alternative medicine , pathology , computer science , programming language
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.