A new family of relatively stable Cr(V) complexes, [Cr(V)O(L)(2)](-) (LH(2) = RC(O)NHOH, R = Me, Ph, 2-HO-Ph, or HONHC(O)(CH(2))(6)), has been obtained by the reactions of hydroxamic acids with Cr(VI) in polar aprotic solvents. Similar reactions in aqueous solutions led to the formation of transient Cr(V) species. All complexes have been characterized by electron paramagnetic resonance spectroscopy and electrospray mass spectrometry. A Cr(V) complex of benzohydroxamic acid (1, R = Ph) was isolated in a pure form (as a K(+) salt) and was characterized by X-ray absorption spectroscopy and analytical techniques. Multiple-scattering analysis of X-ray absorption fine structure spectroscopic data for 1 (solid, 10 K) point to a distorted trigonal-bipyramidal structure with trans-oriented Ph groups and Cr-ligand bond lengths of 1.58 A (Cr-O), 1.88 A (Cr-O(C)), and 1.98 A (Cr-O(N)). Under ambient conditions, 1 is stable for days in aprotic solvents but decomposes within minutes in aqueous solutions (maximal stability at pH approximately 7), which leads predominantly to the formation of Cr(III) complexes. Complex 1 readily undergoes ligand-exchange reactions with biological 1,2-diols, including D-glucose and mucin, in neutral aqueous solutions. It differs from most other types of Cr(V) complexes in its biological activity, since no oxidative cleavage of plasmid DNA in vitro and no significant bacterial mutagenicity (in the TA 102 strain of Salmonella typhimurium) was observed for 1. In natural systems, stabilization of Cr(V) by hydroxamato ligands from bacterial-derived siderophores (followed by ligand-exchange reactions with more abundant carbohydrate ligands) may occur during the biological reduction of Cr(VI) in contaminated soils.