Department of Chemistry and Biochemistry, New Mexico State University, Las Cruces New Mexico 88003, USA.
J Am Chem Soc. 2012 Apr 18;134(15):6516-9. doi: 10.1021/ja211882e. Epub 2012 Apr 4.
The reaction of TEMPO with the iron(I) synthon PhB(MesIm)(3)Fe(COE) leads to formation of the κ(1)-TEMPO complex PhB(MesIm)(3)Fe(TEMPO). Structural and spectroscopic data establish the complex contains divalent iron bound to a nitroxido anion and is isoelectronic to an iron(II) peroxo complex. Thermolysis of the complex results in N-O bond homolysis, leading to the formation of an iron(III) oxo intermediate. The oxo intermediate is active in oxygen atom transfer reactions and can be trapped by the triphenylmethyl radical to give the iron(II) alkoxo complex PhB(MesIm)(3)Fe(OCPh(3)).
TEMPO 与铁(I)配合物 PhB(MesIm)(3)Fe(COE)反应生成了 κ(1)-TEMPO 配合物 PhB(MesIm)(3)Fe(TEMPO)。结构和光谱数据表明，该配合物含有与氮氧自由基配位的二价铁，与铁(II)过氧配合物等电子。该配合物的热解导致 N-O 键均裂，生成铁(III)氧代中间物。该氧代中间物可参与氧原子转移反应，并可被三苯甲基自由基捕获，生成铁(II)烷氧基配合物 PhB(MesIm)(3)Fe(OCPh(3))。
