Unexpected kinetic complexity in the formation of a nonheme oxoiron(IV) complex.
The stoichiometric formation of [FeIV(O)(TPA)(NCMe)]2+ (TPA = tris(2-pyridylmethyl)amine) from the reaction of [FeII(TPA)(NCMe)2]2+ with 1 equiv. peracetic acid exhibits more kinetic complexity than might be expected from the simple stoichiometry. A multiple-pathway mechanism with an FeIV-peracetic acid species, [(TPA)FeIV(O)((H)O3CR)]2+/+, as the primary oxidant is proposed.
Shan
Xiaopeng
X
Department of Chemistry and Center for Metals in Biocatalysis, University of Minnesota, Minneapolis, Minnesota 55455, USA.
Que
Lawrence
L
D000097:Acetonitriles / Q000737:chemistry; D040761:Biomimetic Materials / Q000737:chemistry*; D007501:Iron / Q000737:chemistry*; D007700:Kinetics; D019159:Nonheme Iron Proteins / Q000737:chemistry*; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction
D000097:Acetonitriles; D019159:Nonheme Iron Proteins; D009942:Organometallic Compounds; C473935:oxotris(2-pyridylmethyl)amineiron(IV); D007501:Iron