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DOE OSTI · 2575826

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.
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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 = 1/2). 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. Here, 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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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRYChemistryazidesbridging ligandscluster compoundsheterometallicredox isolation

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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.. 2023-10-13. Lewis Acid Supported Nickel Nitrenoids. https://doi.org/10.1002/anie.202313156

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