Lewis Acid Supported Nickel Nitrenoids

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.

doi:10.1002/ange.202313156

Title: Lewis Acid Supported Nickel Nitrenoids

Journal Article · 08 November 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202313156 · OSTI ID:2216964

Juda, Cristin E. ^[1]; Casaday, Claire E. ^[1]; Clarke, Ryan M. ^[1]; Litak, Nicholas P. ^[1]; Campbell, Brandon M. ^[1]; Chang, Tieyan ^[2]; Zheng, Shao‐Liang ^[1]; Chen, Yu‐Sheng ^[2];

^[1]

Department of Chemistry and Chemical Biology Harvard University 12 Oxford St Cambridge MA 02138 USA
ChemMatCARS Beamline The University of Chicago Advanced Photon Source Argonne IL 60429 USA

Abstract Metalation of the polynucleating ligand ^F,tbs LH ₆ (1,3,5‐C ₆ H ₉ (NC ₆ H ₃ −4‐F−2‐NSiMe ₂ ^t Bu) ₃ ) with two equivalents of Zn(N(SiMe ₃ ) ₂ ) ₂ affords the dinuclear product ( ^F,tbs LH ₂ )Zn ₂ ( 1 ), which can be further deprotonated to yield ( ^F,tbs L)Zn ₂ Li ₂ (OEt ₂ ) ₄ ( 2 ). Transmetalation of 2 with NiCl ₂ (py) ₂ yields the heterometallic, trinuclear cluster ( ^F,tbs L)Zn ₂ Ni(py) ( 3 ). Reduction of 3 with KC ₈ affords [KC ₂₂₂ ][( ^F,tbs L)Zn ₂ Ni] ( 4 ) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to 4 generates the bridging μ ³ ‐nitrenoid adduct [K(THF) ₃ ][( ^F,tbs L)Zn ₂ Ni(μ ³ ‐NAd)] ( 5 ). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state ( S = ). Cyclic voltammetry of 5 reveals two fully reversible redox events. The dianionic nitrenoid [K ₂ (THF) ₉ ][( ^F,tbs L)Zn ₂ Ni(μ ³ ‐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 [Zn ₂ Ni] nitrenoid complexes. However, DFT analysis suggests Ni‐borne oxidation for 5 .

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0008313

OSTI ID:: 2216964

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 50 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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