TY - JOUR
T1 - Delocalization over the heme and the axial ligands of one of the two oxidizing equivalents stored above the ferric state in the peroxidase and catalase Compound-I intermediates: Indirect participation of the proximal axial ligand of iron in the oxidation reactions catalyzed by heme-based peroxidases and catalases?
AU - Weiss, Raymond
AU - Mandon, Dominique
AU - Wolter, Thomas
AU - Trautwein, Alfred X.
AU - Müther, Markus
AU - Bill, Eckhard
AU - Gold, Avram
AU - Jayaraj, Karupiah
AU - Terner, James
PY - 1996/8/1
Y1 - 1996/8/1
N2 - A comparison of the exchange interactions arising in the peroxidase and catalase Compound I intermediates and their iron(IV)-oxo porphyrin π-cation radical models, both of which are two oxidizing equivalents above the ferric state, suggests that in the models the oxidizing equivalent is localized on the porphyrin ring, while in the proteins it is partly delocalized onto the proximal ligand. Thus, the proximal axial ligand of iron participates indirectly in the oxidation reactions catalyzed by the enzymes. Possible roles of the axial ligand in the catalytic mechanism of these heme-based enzymes are discussed.
AB - A comparison of the exchange interactions arising in the peroxidase and catalase Compound I intermediates and their iron(IV)-oxo porphyrin π-cation radical models, both of which are two oxidizing equivalents above the ferric state, suggests that in the models the oxidizing equivalent is localized on the porphyrin ring, while in the proteins it is partly delocalized onto the proximal ligand. Thus, the proximal axial ligand of iron participates indirectly in the oxidation reactions catalyzed by the enzymes. Possible roles of the axial ligand in the catalytic mechanism of these heme-based enzymes are discussed.
UR - http://www.scopus.com/inward/record.url?scp=0001595329&partnerID=8YFLogxK
U2 - 10.1007/s007750050069
DO - 10.1007/s007750050069
M3 - Scientific review articles
AN - SCOPUS:0001595329
SN - 0949-8257
VL - 1
SP - 377
EP - 383
JO - Journal of Biological Inorganic Chemistry
JF - Journal of Biological Inorganic Chemistry
IS - 4
ER -