Effect of anions on redox reactions. 1. Chromium(II) reduction of bis(pentane-2,4-dionato)(ethylenediamine)cobalt(III) in the presence of chloride ions

Nita Lewis, Ananda M. Ray

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Abstract

The effect of chloride ions on the Cr(II) reduction of [Co(en)(ptdn)2]+ was studied. The rate for the outer-sphere pathway was twice that of the uncatalyzed reaction (k(25.0°C) = (4.86 ± 0.04) × 10-3 M-1 s-1, ΔH = 17 ± 1 kcal mol-1, ΔS = -13 ± 3 eu) whereas the rates for the inner-sphere pathways were practically unaffected. The kinetic parameters for the monobridged pathway were k(25.0°C) = (2.97 ± 0.02) × 10-3 M-1 s-1, and those of the dibridged path were k(25.0 °C) = (1.46 ± 0.02) × 10-3 M-1 s-1, ΔH = 13 ± 1 kcal mol-1, and ΔS = -27 ± 1 eu. No chloride could be detected in the inner-sphere electron-transfer products.

Original languageEnglish
Pages (from-to)3649-3653
Number of pages5
JournalInorganic Chemistry
Volume23
Issue number22
StatePublished - Dec 1 1984
Externally publishedYes

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ethylenediamine
Redox reactions
pentanes
Chromium
Cobalt
Anions
Chlorides
chromium
cobalt
chlorides
Ions
anions
ions
Kinetic parameters
electron transfer
Electrons
kinetics
products
pentane

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Effect of anions on redox reactions. 1. Chromium(II) reduction of bis(pentane-2,4-dionato)(ethylenediamine)cobalt(III) in the presence of chloride ions",
abstract = "The effect of chloride ions on the Cr(II) reduction of [Co(en)(ptdn)2]+ was studied. The rate for the outer-sphere pathway was twice that of the uncatalyzed reaction (k(25.0°C) = (4.86 ± 0.04) × 10-3 M-1 s-1, ΔH‡ = 17 ± 1 kcal mol-1, ΔS‡ = -13 ± 3 eu) whereas the rates for the inner-sphere pathways were practically unaffected. The kinetic parameters for the monobridged pathway were k(25.0°C) = (2.97 ± 0.02) × 10-3 M-1 s-1, and those of the dibridged path were k(25.0 °C) = (1.46 ± 0.02) × 10-3 M-1 s-1, ΔH‡ = 13 ± 1 kcal mol-1, and ΔS‡ = -27 ± 1 eu. No chloride could be detected in the inner-sphere electron-transfer products.",
author = "Nita Lewis and Ray, {Ananda M.}",
year = "1984",
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pages = "3649--3653",
journal = "Inorganic Chemistry",
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publisher = "American Chemical Society",
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TY - JOUR

T1 - Effect of anions on redox reactions. 1. Chromium(II) reduction of bis(pentane-2,4-dionato)(ethylenediamine)cobalt(III) in the presence of chloride ions

AU - Lewis, Nita

AU - Ray, Ananda M.

PY - 1984/12/1

Y1 - 1984/12/1

N2 - The effect of chloride ions on the Cr(II) reduction of [Co(en)(ptdn)2]+ was studied. The rate for the outer-sphere pathway was twice that of the uncatalyzed reaction (k(25.0°C) = (4.86 ± 0.04) × 10-3 M-1 s-1, ΔH‡ = 17 ± 1 kcal mol-1, ΔS‡ = -13 ± 3 eu) whereas the rates for the inner-sphere pathways were practically unaffected. The kinetic parameters for the monobridged pathway were k(25.0°C) = (2.97 ± 0.02) × 10-3 M-1 s-1, and those of the dibridged path were k(25.0 °C) = (1.46 ± 0.02) × 10-3 M-1 s-1, ΔH‡ = 13 ± 1 kcal mol-1, and ΔS‡ = -27 ± 1 eu. No chloride could be detected in the inner-sphere electron-transfer products.

AB - The effect of chloride ions on the Cr(II) reduction of [Co(en)(ptdn)2]+ was studied. The rate for the outer-sphere pathway was twice that of the uncatalyzed reaction (k(25.0°C) = (4.86 ± 0.04) × 10-3 M-1 s-1, ΔH‡ = 17 ± 1 kcal mol-1, ΔS‡ = -13 ± 3 eu) whereas the rates for the inner-sphere pathways were practically unaffected. The kinetic parameters for the monobridged pathway were k(25.0°C) = (2.97 ± 0.02) × 10-3 M-1 s-1, and those of the dibridged path were k(25.0 °C) = (1.46 ± 0.02) × 10-3 M-1 s-1, ΔH‡ = 13 ± 1 kcal mol-1, and ΔS‡ = -27 ± 1 eu. No chloride could be detected in the inner-sphere electron-transfer products.

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