Oxidative Ligand Rearrangement Due to Incipient Aminyl Radicals in the Oxidation of Iron(II) Species with Dioxygen

Abstract

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.

Department(s)

Chemistry

Sponsor(s)

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)

1434-1948

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2008 Wiley-VCH Verlag Berlin, All rights reserved.

Publication Date

01 Feb 2008

Link to Full Text

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