Oxidative Ligand Rearrangement Due to Incipient Aminyl Radicals in the Oxidation of Iron(II) Species with Dioxygen
The ferrous complex [(L1)FeII-THF]-, featuring the trisamidoamine ligand [(RNC6H4) 3N]3-, where R is the electron-rich 4-tBu-Ph moiety, can undergo a one-electron oxidation by dioxygen to afford the corresponding [(L1)FeIII-OH]- complex, and a parallel two-electron oxidation to generate the antiferromagnetically coupled diferric μ -oxo compound [(L1 re-1)Fe-O-Fe(L1 re-1)]. The latter compound possesses a ligand that exhibits oxidative rearrangement and retention of the oxidation equivalent in a o-diiminobenzosemiquinato moiety as a π radical. Ligand oxidation is perceived to initiate at an amido residue leading to formation of an electrophilic, metal-bould aminyl radical that undergoes an 1,4-(N-to-N) aryl migration reaction.
R. Çelenligil-Çetin et al., "Oxidative Ligand Rearrangement Due to Incipient Aminyl Radicals in the Oxidation of Iron(II) Species with Dioxygen," European Journal of Inorganic Chemistry, no. 5, pp. 673-677, Wiley-VCH Verlag Berlin, Feb 2008.
The definitive version is available at http://dx.doi.org/10.1002/ejic.200701297
National Institutes of Health (U.S.)
National Science Foundation (U.S.)
Keywords and Phrases
Iron; N Ligands; Radicals; Rearrangements (Chemistry); Tripodal Ligands
International Standard Serial Number (ISSN)
Article - Journal
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