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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Selective C-H Bond Cleavage with a High-Spin FeIV-Oxido Complex
Chen Sun1, Jennifer L Jaimes1, Alec H Follmer1
1Department of Chemistry, University of California-Irvine, Irvine, CA 92697, USA.
Abstract:
Non-heme Fe monooxygenases activate C-H bonds using intermediates with high-spin FeIV-oxido centers. To mimic these sites, a new tripodal ligand [pop]3- was prepared that contains three phosphoryl amido groups that are capable of stabilizing metal centers in high oxidation states. The ligand was used to generate [FeIVpop(O)]-, a new FeIV-oxido complex with an S = 2 spin ground state. Spectroscopic measurements, which included low-temperature absorption and electron paramagnetic resonance spectroscopy, supported the assignment of a high-spin FeIV center. The complex showed reactivity with benzyl alcohol as the external substrate but not with related compounds (e.g., ethyl benzene and benzyl methyl ether), suggesting the possibility that hydrogen bonding interaction(s) between the substrate and [FeIVpop(O)]- was necessary for reactivity. These results exemplify the potential role of the secondary coordination sphere in metal-mediated processes.
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