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

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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.

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ASJC Scopus subject areas

  • Inorganic Chemistry

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