TY - JOUR
T1 - Characterization of a high-spin non-heme FeIII-OOH intermediate and its quantitative conversion to an FeIV=O complex
AU - Li, Feifei
AU - Meier, Katlyn K.
AU - Cranswick, Matthew A.
AU - Chakrabarti, Mrinmoy
AU - Van Heuvelen, Katherine M.
AU - Münck, Eckard
AU - Que, Lawrence
PY - 2011/5/18
Y1 - 2011/5/18
N2 - We have generated a high-spin FeIII-OOH complex supported by tetramethylcyclam via protonation of its conjugate base and characterized it in detail using various spectroscopic methods. This FeIII-OOH species can be converted quantitatively to an FeIV=O complex via O-O bond cleavage; this is the first example of such a conversion. This conversion is promoted by two factors: the strong FeIII-OOH bond, which inhibits Fe-O bond lysis, and the addition of protons, which facilitates O-O bond cleavage. This example provides a synthetic precedent for how O-O bond cleavage of high-spin FeIII-peroxo intermediates of non-heme iron enzymes may be promoted.
AB - We have generated a high-spin FeIII-OOH complex supported by tetramethylcyclam via protonation of its conjugate base and characterized it in detail using various spectroscopic methods. This FeIII-OOH species can be converted quantitatively to an FeIV=O complex via O-O bond cleavage; this is the first example of such a conversion. This conversion is promoted by two factors: the strong FeIII-OOH bond, which inhibits Fe-O bond lysis, and the addition of protons, which facilitates O-O bond cleavage. This example provides a synthetic precedent for how O-O bond cleavage of high-spin FeIII-peroxo intermediates of non-heme iron enzymes may be promoted.
UR - http://www.scopus.com/inward/record.url?scp=79955879210&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=79955879210&partnerID=8YFLogxK
U2 - 10.1021/ja111742z
DO - 10.1021/ja111742z
M3 - Article
C2 - 21517091
AN - SCOPUS:79955879210
SN - 0002-7863
VL - 133
SP - 7256
EP - 7259
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 19
ER -