Synthesis And Reactivity Of Bis(amido)-Arsorene-iron(?) Complexes

This dissertation describes the synthesis,characterization,and reactivity of the first iminoarsorane-transition-metal complex [(?-N,N,N-dfpN2 As NDipp)Fe(THF)](3).1.Synthesis and characterization of iron(II)complexes with bis(anilido)ligation and iminoarsorane ligation.Treatment of(2,6-F2C6H3)(2-Br C6H4)NH with two equiv.of BunLi,followed by the interaction with 0.5 equiv.of Ph As Cl2 and quenching with aqueous solution,afforded the new bis(amido)-arsorane ligand((o-(N-(2,6-F2C6H3)NH)C6H4)2As Ph(denoted as H2(dfpN2As)).The interaction of H2(dfpN2As))with 0.5 equiv.of [Fe(N(TMS)2)2]2 resulted in amine elimination and gave the bis(amido)-arsorene-iron(II)complex [(?-N,N,Asdfp N2As)Fe(THF)2](1).Further treatment of 1 with the organic azide Dipp N3 rendered the formation of the first iminoarsorane-transition-metal complex [(?-N,N,NdfpN2 As NDipp)Fe(THF)](3)as an air-and moisture-sensitive green solid.These complexes were characterized by single-crystal X-Ray diffraction,EA,1H NMR,solution magnetic susceptibility measurement,FT-IR,absorption spectrum and 57 Fe M?ssbauer spectrum.2.Reactivity and catalytic applications of the first iminoarsorane-transition-metal complex.Reactivity study indicated that 3 can undergo nitrene-transfer reactions with excess amounts of 2,6-dimethylphenylisocyanide and PPh3 to produce the nitrene-transfer products Dipp NCNC6H3Me2-2,6 and Ph3PCNC6H3Me2-2,6,respectively and the corresponding bis(amido)-arsorane-iron(II)complexes [(?-N,N,As-dfpN2As)Fe(CNC6H3Me2-2,6)3](6)and [(?-N,N,As-dfpN2As)Fe(PPh3)](7).The molecular structure of 6 has been characterized by singlecrystal X-ray diffraction studies.These complexes were fully characterized by various spectroscopic methods.The bis(anilido)-imino-arsorane-iron(II)complexes and iminoarsorane--iron(II)complex can catalyze intramolecular aliphatic C-H bond amination reaction of 1-azido-2-phenethylbenzene and(4-azido-4-methylpentyl)benzene or intramolecular hydrogen transfer reaction of 2-azido-1,3-diisopropylbenzene and(4-azidobutyl)benzene.High-valent iron imido species were probable intermediates.