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Abstract Metalation of the polynucleating ligandF,tbsLH6(1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2affords the dinuclear product (F,tbsLH2)Zn2(1), which can be further deprotonated to yield (F,tbsL)Zn2Li2(OEt2)4(2). Transmetalation of2with NiCl2(py)2yields the heterometallic, trinuclear cluster (F,tbsL)Zn2Ni(py) (3). Reduction of3with KC8affords [KC222][(F,tbsL)Zn2Ni] (4) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to4generates the bridging μ3‐nitrenoid adduct [K(THF)3][(F,tbsL)Zn2Ni(μ3‐NAd)] (5). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state (S=). Cyclic voltammetry of5reveals two fully reversible redox events. The dianionic nitrenoid [K2(THF)9][(F,tbsL)Zn2Ni(μ3‐NAd)] (6) was isolated and characterized while the neutral redox isomer was observed to undergo both intra‐ and intermolecular H‐atom abstraction processes. Ni K‐edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn2Ni] nitrenoid complexes. However, DFT analysis suggests Ni‐borne oxidation for5.
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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). 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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- Award ID(s):
- 1834750
- PAR ID:
- 10089196
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- Angewandte Chemie
- Volume:
- 131
- Issue:
- 17
- ISSN:
- 0044-8249
- Page Range / eLocation ID:
- p. 5743-5747
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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