Lewis Acid Supported Nickel Nitrenoids |
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| Authors: | Dr Cristin E Juda Claire E Casaday Dr Ryan M Clarke Nicholas P Litak Brandon M Campbell Tieyan Chang Dr Shao-Liang Zheng Dr Yu-Sheng Chen Dr Theodore A Betley |
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| Institution: | 1. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St, Cambridge, MA 02138 USA
These authors contributed equally.;2. Department of Chemistry and Chemical Biology, Harvard University, 12 Oxford St, Cambridge, MA 02138 USA;3. ChemMatCARS Beamline, The University of Chicago, Advanced Photon Source, Argonne, IL 60429 USA |
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| Abstract: | 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 =  ). 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 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 for 5 . |
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| Keywords: | Azides Bridging Ligands Cluster Compounds Heterometallic Redox Isolation |
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