Volumes of activation for dissociative (D) mechanisms

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Title Volumes of activation for dissociative (D) mechanisms: the substitution of pentacyanoferrate complexes by various nucleophiles
Author(s) T. R. Sullivan, D. R. Stranks, J. Burgess, Robert I. Haines
Journal Journal of the Chemical Society, Dalton Transactions
Date 1977
Volume
Issue 15
Start page 1460
End page 1466
Abstract The dissociative step of a dissociative, or D, substitution mechanism exhibits a volume of activation, V1, which is independent of the nature of the incoming nucleophile. For the reaction of [Fe(CN)5(3,5Me2-py)]3?(3,5Me2-py = 3,5-dimethylpyridine) with [CN]?, V1= 20.5 ? 0.8 cm3 mol?1; with pyrazine, V1= 21.2 ? 1.0 cm3 mol?1; and with imidazole, V1= 20.3 ? 1.0 cm3 mol?1. For the reaction of [Fe(CN)5(3CN-py)]3?(3CN-py = 3-cyano-pyridine) with [CN]?, V1= 20.6 ? 0.5 cm3 mol?1. These volumes of activation are shown to correspond to stretching of the Fe?N bond in the activated complex from 65 to 88% of the distance corresponding to complete dissociation of the leaving group from the [Fe(CN)5]3? moiety
DOI 10.1039/DT9770001460
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