The vanadium(II) reduction of tris(2,2′-bipyridine)cobalt(III) and the dissociation of the tris(2,2′-bipyridine)cobalt(II) product
- 1 January 1972
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 11,p. 1171-1176
- https://doi.org/10.1039/dt9720001171
Abstract
The rate law for the vanadium(II) reduction of Co(bipy)3 3+(bipy = 2,2′-bipyridine), is independent of hydrogen-ion concentration and of the form, rate =k[V2+][Co(bipy)3 3+]. At 25 °C and µ= 2·0M(LiClO4), k= 1110 l mol–1 s–1ΔH‡= 3·6 ± 0·1 kcal mol–1, and ΔS‡=–32·6 ± 0·4 e.u. The reaction is of the outer-sphere type. The subsequent dissociation (by aquation) of the product Co(bipy)3 2+ has also been studied and the mechanism is discussed. At 25° the rate constant k1 for cleavage of the first chelate ring is 36·0 s–1, ΔH‡1= 12·4 ± 0·4 kcal mol–1, and ΔS‡1=–10·0 ± 1·6 e.u., µ= 2·0M(LiClO4). Activation parameters are compared with those for the corresponding dissociations of Fe(bipy)3 2+ and Ni(bipy)3 2+.Keywords
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