EPR characterisation of the CrV intermediates in the CrVI/V oxidations of organic substrates and of relevance to Cr-induced cancers

Abstract

An empirical method has been developed for determining the coordination number of CrV complexes (five- or six-coordinate) and the donor groups bound to CrV from the measured giso and Aiso values. The giso values depend only on the nature of the donor groups and the number of each group, which is very useful in the characterisation of the coordination number and donors. By contrast, the Aiso values appear to be sensitive to the nature of the equatorial donor atoms and the coordination geometry. Strong correlations have been found between the giso values of isoelectronic CrV and VIV complexes and between the Aiso values of analogous complexes of these two metal ions. These, combined, have been used to understand the solution chemistry of CrV using EPR spectroscopy. Such studies have also been invaluable in unravelling the biochemistry that occurs in cell media and cells exposed to carcinogenic CrVI and, hence, possible mechanisms of Cr-induced cancers.