Title:
Oxidative ligand rearrangement due to incipient aminyl radicals in the
oxidation of iron(II) species with dioxygen
Languages of Item:
English
Abstract:
The ferrous complex [(L-1)Fe-II-THF](-), featuring the trisamido-amine
ligand [(RNC6H4)(3)N](3-), where R is the electron-rich 4-tBu-Ph
moiety, can undergo a one-electron oxidation by dioxygen to afford the
corresponding [(L-1)Fe-III-OH](-) complex, and a parallel two-electron
oxidation to generate the antiferromagnetically coupled diferric mu-oxo
compound [(L-re-1(1))Fe-O-Fe(L-re-1(1))]. The latter compound
possesses a ligand that exhibits oxidative rearrangement and retention
of the oxidation equivalent in a o-diiminobenzosemiquinato moiety as a
pi 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. ((c)
Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008).
Authors:
Celenligil-Cetin, Remle
Paraskevopoulou, Patrina
Dinda, Rupam
and Lalioti, Nikolia
Sanakis, Yiannis
Rawashdeh, Abdel Monem and
Staples, Richard J.
Sinn, Ekkehard
Stavropoulos, Pericles
Journal:
European Journal of Inorganic Chemistry
Publisher:
WILEY-V C H VERLAG GMBH
Keywords:
iron; N ligands; radicals; rearrangement; tripodal ligands
Main subject category:
Science
