Evidence for Cu-O2 intermediates in superoxide oxidations by biomimetic copper(II) complexes

Journal of the American Chemical Society
Valeriy V Smirnov, Justine P Roth

Abstract

The mechanism by which [Cu(II)(L)](OTf)2 and [Cu(II)N3(L)](OTf) (L = TEPA: tris(2-pyridylethyl)amine or TMPA: tris(2-pyridylmethyl)amine; OTf = trifluoromethanesulfonate) react with superoxide (O2*-) to form [Cu(I)(L)](OTf) and O2 is described. Evidence for a CuO2 intermediate is presented based on stopped-flow experiments and competitive oxygen (18O) kinetic isotope effects on the bimolecular reactions of (16,16)O2*- and (18,16)O2*- ((16,16)k/(18,16)k). The (16,16)k/(18,16)k fall within a narrow range from 0.9836 +/- 0.0043 to 0.9886 +/- 0.0078 for reactions of copper(II) complexes with different coordination geometries and redox potentials that span a 0.67 V range. The results are inconsistent with a mechanism that involves either rate-determining O2*- binding or one-step electron transfer. Rather a mechanism involving formation of a CuO2 intermediate prior to the loss of O2 in the rate-determining step is proposed. Calculations of similar inverse isotope effects, using stretching frequencies of CuO2 adducts generated from copper(I) complexes and O2, suggest that the intermediate has a superoxo structure. The use of 18O isotope effects to relate activated oxygen intermediates in enzymes to those derived from inorganic compoun...Continue Reading

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Citations

Jun 28, 2008·Journal of the American Chemical Society·Arnab MukherjeeJustine P Roth
Jun 14, 2012·Physical Chemistry Chemical Physics : PCCP·Yusuke YamadaShunichi Fukuzumi
Jan 20, 2017·Chemical Reviews·Courtney E ElwellWilliam B Tolman
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Jan 8, 2011·Physical Chemistry Chemical Physics : PCCP·Tomonori KawashimaShunichi Fukuzumi
Jan 8, 2021·Journal of Biological Inorganic Chemistry : JBIC : a Publication of the Society of Biological Inorganic Chemistry·Mariappan MuraliBalasubramaniam Selvakumaran
Jan 6, 2009·The Journal of Physical Chemistry. a·Valeriy V SmirnovJustine P Roth
Nov 30, 2006·Langmuir : the ACS Journal of Surfaces and Colloids·Bineta KeitaRobila Belghiche
Apr 13, 2010·Inorganic Chemistry·Daniel C AshleyJustine P Roth
Dec 21, 2006·Journal of the American Chemical Society·Valeriy V Smirnov, Justine P Roth
Dec 15, 2006·Journal of the American Chemical Society·Michael P Lanci, Justine P Roth

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