Influence of oxygen insertion on the electrochemistry of chromium(III) dithiocarbamate complexes

A. M. Bond, G. G. Wallace

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Abstract

Dithiocarbamate (dtc) complexes of chromium(III) containing oxygen-expanded ligands, odtc, can be synthesized. With pyrrolidine-TV-carbodithioate ([pdtc]-) as the dithiocarbamate ligand, the electrochemistry of both Cr(pdtc)3 and Cr(pdtc)2(opdtc) has been examined in detail. On the basis of studies employing cyclic and differential-pulse voltammetry at platinum, gold, and glassy-carbon electrodes in methanol, acetone, acetonitrile, and dichloromethane, it has been shown that the formally chromium(IV) complex, [Cr(pdtc)2(opdtc)]+, is kinetically more stable than [Cr(pdtc)3]+. Thermodynamically, the same stability order also applies in the sense that Cr(pdtc)2(opdtc) is easier to oxidize than Cr(pdtc)3. The enhanced stability is attributed to the increased importance of the resonance form.

Original languageEnglish
Pages (from-to)1858-1865
Number of pages8
JournalInorganic Chemistry
Volume23
Issue number13
DOIs
Publication statusPublished - Jan 1984
Externally publishedYes

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