Synthesis of two-coordinate iron aryloxides and their reactions with organic azide: Intramolecular C-H bond amination |
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| Authors: | Tsubasa Hatanaka |
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| Institution: | Department of Chemistry, Tokyo Institute of Technology, Ookayama, Meguro-ku, Tokyo 152-8551, Japan |
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| Abstract: | The synthesis and reaction of homoleptic iron(II) complexes with 2,6-di-adamantyl-substituted aryloxides OC6H2-2,6-Ad-4-R]− (OArAdR]−, Ad = adamantyl, R = Me, iPr) are described. Monomeric two-coordinate iron aryloxides Fe(OArAdR)2 (R = Me, 1; iPr, 2) were synthesized by the reaction of FeN(SiMe3)2]2 with 2 equiv of HOArAdR. Treatment of 1 and 2 with 1-azidoadamantane resulted in intramolecular insertion of an adamantyl nitrene into a methylene C-H bond of the aryloxide adamantyl substituent, yielding the corresponding amine-aryloxide complexes Fe(OArAdR)(OArAdR-NHAd) (R = Me, 3; iPr, 4). Molecular structures of all these complexes are reported. |
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| Keywords: | Low-coordinate complexes Aryloxide C-H activation Imido complexes Steric effect Iron |
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