Lewis Acid Supported Nickel Nitrenoids

Metalation of the polynucleating ligand F,tbsLH6 (1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2 affords the dinuclear product (F,tbsLH2)Zn2 (1), which can be further deprotonated to yield (F,tbsL)Zn2Li2(OEt2)4 (2). Transmetalation of 2 with NiCl2(py)2 yields the heterome...

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Bibliographic Details
Published in:Angewandte Chemie International Edition 2023-12, Vol.62 (50), p.e202313156-n/a
Main Authors: Juda, Cristin E., Casaday, Claire E., Clarke, Ryan M., Litak, Nicholas P., Campbell, Brandon M., Chang, Tieyan, Zheng, Shao‐Liang, Chen, Yu‐Sheng, Betley, Theodore A.
Format: Article
Language:English
Subjects:
Azides
Bridging Ligands
Cluster Compounds
Clusters
Heterometallic
Lewis acid
Nickel
Nickel chloride
Organic compounds
Oxidation
Redox Isolation
Spectroscopy
Valence
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Summary:Metalation of the polynucleating ligand F,tbsLH6 (1,3,5‐C6H9(NC6H3−4‐F−2‐NSiMe2tBu)3) with two equivalents of Zn(N(SiMe3)2)2 affords the dinuclear product (F,tbsLH2)Zn2 (1), which can be further deprotonated to yield (F,tbsL)Zn2Li2(OEt2)4 (2). Transmetalation of 2 with NiCl2(py)2 yields the heterometallic, trinuclear cluster (F,tbsL)Zn2Ni(py) (3). Reduction of 3 with KC8 affords [KC222][(F,tbsL)Zn2Ni] (4) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to 4 generates 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 = 1/2 ${{ 1/2 }}$ ). Cyclic voltammetry of 5 reveals 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 ion 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 for 5. Stepwise metalation of a polynucleating ligand generated heterobimetallic clusters featuring two redox inactive Lewis acids (Zn2+) and one transition metal (Ni). Reduction of the [Zn2Ni] cluster and reaction with a nitrene transfer reagent yielded [K(THF)3][(F,tbsL)Zn2Ni(μ3‐NAd)]. Ni K‐edge XAS (X‐ray absorption spectroscopy) studies support the assignment of the primary redox pair as a divalent nickel coupled to an imidyl ligand.
ISSN:1433-7851
1521-3773
DOI:10.1002/anie.202313156