Measured rates of fluoride/metal association correlate with rates of superoxide/metal reactions for Fe(III)EDTA(H2O)- and related complexes

Journal of the American Chemical Society
Jack S SummersJamie R Jones

Abstract

The effects of 10 paramagnetic metal complexes (Fe(III)EDTA(H2O)-, Fe(III)EDTA(OH)2-, Fe(III)PDTA-, Fe(III)DTPA2-, Fe(III)2O(TTHA)2-, Fe(III)(CN)6(3-), Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, Mn(II)beta-EDDADP2-, and Mn(II)PO4(-)) on F- ion 19F NMR transverse relaxation rates (R2 = 1/T2) were studied in aqueous solutions as a function of temperature. Consistent with efficient relaxation requiring formation of a metal/F- bond, only the substitution inert complexes Fe(III)(CN)6(3-) and Fe(III)EDTA(OH)2- had no measured effect on T2 relaxation of the F- 19F resonance. For the remaining eight complexes, kinetic parameters (apparent second-order rate constants and activation enthalpies) for metal/F- association were determined from the dependence of the observed relaxation enhancements on complex concentration and temperature. Apparent metal/F- association rate constants for these complexes (k(app,F-)) spanned 5 orders of magnitude. In addition, we measured the rates at which O2*- reacts with Fe(III)PDTA-, Mn(II)EDTA(H2O)2-, Mn(II)PDTA2-, and Mn(II)beta-EDDADP2- by pulse radiolysis. Although no intermediate is observed during the reduction of Fe(III)PDTA- by O2*-, each of the Mn(II) complexes reacts with formation of a transient intermedia...Continue Reading

References

Jul 21, 1977·Biochimica Et Biophysica Acta·Y A Ilan, G Czapski
Dec 1, 1992·Journal of Inorganic Biochemistry·T J EganP Aisen
Jun 9, 2005·Chemical Reviews·Lothar Helm, André E Merbach
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Citations

Aug 7, 2013·Environmental Science & Technology·Kathrin WuttigPeter L Croot
Feb 3, 2011·Inorganic Chemistry·Elaine NamJulie A Kovacs
Sep 6, 2011·Inorganic Chemistry·Qiao ZhangChristian R Goldsmith
Jul 26, 2017·Organic & Biomolecular Chemistry·Qiaoli PengZhong-Xing Jiang

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