Influence of acetate ion on the formation reactions of organochromium(III) species. A rapid-scan and high-pressure pulse-radiolysis study

Wolfgang Gaede, Achim Gerhard, Rudi Van Eldik, Haim Cohen, Dan Meyerstein

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7 Scopus citations

Abstract

A UV/VIS rapid-scan technique was employed to study the formation of organochromium(III) species that are characterized by absorbance maxima at 321 and 412 nm. The effect of acetate on this formation reaction was studied, and spectral measurements demonstrated that it is mainly the monomeric chromium(II) acetate species that react with the alkyl radical, no involvement of the dimeric species being found. A high-pressure pulse-radiolysis technique was employed to study the effect of pressure on the formation of such complexes. The observed volumes of activation exhibit a decrease from +5.7 to -7.4 cm3 mol-1 on increasing the acetate concentration from 0 to 0.27 mol dm-3. Similar measurements in the presence of phosphate did not indicate any significant effect on the observed volume of activation for the formation of the metal-carbon bond. This difference can be interpreted in terms of the pressure dependence of the dimerization of chromium(II) acetate complexes, which was measured independently and exhibits a reaction volume of +38 ± 4 cm3 mol-1. It is concluded that the mechanism of the formation of chromium-carbon δ bonds is not affected by anions such as acetate and phosphate.

Original languageEnglish
Pages (from-to)2065-2070
Number of pages6
JournalJournal of the Chemical Society. Dalton Transactions
Issue number13
DOIs
StatePublished - 1 Dec 1993

ASJC Scopus subject areas

  • Chemistry (all)

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