TY - JOUR
T1 - Dioxygen activation and catalytic aerobic oxidation by a mononuclear nonheme iron(II) complex
AU - Kim, Sun Ok
AU - Sastri, Chivukula V.
AU - Seo, Mi Sook
AU - Kim, Jinheung
AU - Nam, Wonwoo
PY - 2005/3/30
Y1 - 2005/3/30
N2 - We have used dioxygen, not artificial oxidants such as peracids, iodosylarenes, and hydroperoxides, in the generation of a mononuclear nonheme oxoiron(IV) complex, [Fe(IV)(TMC)(O)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), from its corresponding Fe(II) complex, [Fe(TMC)(CF3SO3)2]. The formation of oxoiron(IV) species by activating dioxygen was markedly dependent on iron(II) complexes and solvents, and this observation was interpreted with the electronic effect of iron(II) complexes on dioxygen activation to form oxoiron(IV) species. A catalytic aerobic oxidation of organic substrates was demonstrated in the presence of the [Fe(TMC)]2+ complex. By carrying out 18O-labeled water experiment, we were able to conclude that the oxidation of organic substrates was mediated by an oxoiron(IV) intermediate, not by a radical type of autoxidation process.
AB - We have used dioxygen, not artificial oxidants such as peracids, iodosylarenes, and hydroperoxides, in the generation of a mononuclear nonheme oxoiron(IV) complex, [Fe(IV)(TMC)(O)]2+ (TMC = 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane), from its corresponding Fe(II) complex, [Fe(TMC)(CF3SO3)2]. The formation of oxoiron(IV) species by activating dioxygen was markedly dependent on iron(II) complexes and solvents, and this observation was interpreted with the electronic effect of iron(II) complexes on dioxygen activation to form oxoiron(IV) species. A catalytic aerobic oxidation of organic substrates was demonstrated in the presence of the [Fe(TMC)]2+ complex. By carrying out 18O-labeled water experiment, we were able to conclude that the oxidation of organic substrates was mediated by an oxoiron(IV) intermediate, not by a radical type of autoxidation process.
UR - http://www.scopus.com/inward/record.url?scp=16244417770&partnerID=8YFLogxK
U2 - 10.1021/ja043083i
DO - 10.1021/ja043083i
M3 - Article
C2 - 15783193
AN - SCOPUS:16244417770
SN - 0002-7863
VL - 127
SP - 4178
EP - 4179
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 12
ER -