Electron transfer. 138. Potentials involving chelated chromium(V)

Electron transfer. 138. Potentials involving chelated chromium(V) The bis(chelated) complex of CrV(0) derived from the dianion (L2 −) of 2-ethyl-2-hydroxybutanoic acid is readily reduced to a bis(chelate of CrIII, featuring the monoanion (LH−) [Cr V(0)(L2−)2]−+4H++H2O+2e−→[CrIII(OH2)2(LH− 2]+ of this acid. Potentials estimated by Ghosh in 1993 for this 2e− change, E0 (pH 0) 1.32 V, Eeff (pH 3.3) 0.93 V, are in accord with the nearly irreversible reductions of the Cr(V) species (in 1∶1 ligand buffer) by Fe2+, V02+, IrCl6 3 − and I−, whereas lower values reported by Bose in 1996, E0 (pH 0) 0.84 V, Eeff (pH 3.3) 0.45 V, are potentiometrically inconsistent with these conversions. A similar discrepancy is noted for potentials for Cr(V,IV) estimated in 1996, E0 (pH 0) 0.84 V, Eeff (pH 3.3) 0.46 V, which, wholly contrary to observation, predict that the reductions of excess Cr(V) to CR(IV) by Fe2+, V02+, and I− are thermodynamically disfavored. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

Electron transfer. 138. Potentials involving chelated chromium(V)

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Publisher
Springer Netherlands
Copyright
Copyright © 1998 by Springer
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1163/156856798X00618
Publisher site
See Article on Publisher Site

Abstract

The bis(chelated) complex of CrV(0) derived from the dianion (L2 −) of 2-ethyl-2-hydroxybutanoic acid is readily reduced to a bis(chelate of CrIII, featuring the monoanion (LH−) [Cr V(0)(L2−)2]−+4H++H2O+2e−→[CrIII(OH2)2(LH− 2]+ of this acid. Potentials estimated by Ghosh in 1993 for this 2e− change, E0 (pH 0) 1.32 V, Eeff (pH 3.3) 0.93 V, are in accord with the nearly irreversible reductions of the Cr(V) species (in 1∶1 ligand buffer) by Fe2+, V02+, IrCl6 3 − and I−, whereas lower values reported by Bose in 1996, E0 (pH 0) 0.84 V, Eeff (pH 3.3) 0.45 V, are potentiometrically inconsistent with these conversions. A similar discrepancy is noted for potentials for Cr(V,IV) estimated in 1996, E0 (pH 0) 0.84 V, Eeff (pH 3.3) 0.46 V, which, wholly contrary to observation, predict that the reductions of excess Cr(V) to CR(IV) by Fe2+, V02+, and I− are thermodynamically disfavored.

Journal

Research on Chemical IntermediatesSpringer Journals

Published: Apr 15, 2009

References

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