Faculty Publications

Title

Kinetics of aquation of tris(methylmalonato)chromate(III) anion in acidic solutions

Document Type

Article

Journal/Book/Conference Title

Journal of Inorganic and Nuclear Chemistry

Volume

34

Issue

1

First Page

221

Last Page

226

Abstract

The aquation of tris(methylmalonato)chromate(III) anion was studied at 25-40° in 0·10-1·0 F HClO4 (μ = 0·20-1·0, NaClO4). The observed pseudo-first order rate constant kobs was found to be dependent on the hydrogen-ion concentration over the entire range of [H+]: kobs = k′[H+] + k″. At 25° k′ = 5·88 × 10-41 mole-1sec-1, and k″ = 0·967 × 10-4 sec-1. Over the temperature range Ea = 22·0 kcal/mol, and log PZ = 16·5. The product of aquation was found to be trans-[Cr(Mmal)2(H2O)2]- (Mmal = methylmalonate), and a mechanism in which a dissociation of the protonated intermediate, [Cr(Mmal)2(HMmal)]2-, followed by a fast attack of two water molecules in opposite directions is proposed. © 1972.

Original Publication Date

1-1-1972

DOI of published version

10.1016/0022-1902(72)80382-8

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