The exceptionally stable cobalt(III)–desferrioxamine B complex

The biogeochemistry of trivalent iron, manganese, and cobalt in the oceans is dominated by soluble complexes formed with high-affinity organic ligands that are believed to be microbial siderophores or similar biogenic chelating agents. Desferrioxamine B (DFOB), a trihydroxamate siderophore found in both terrestrial and marine environments, has served as a useful model for a large class of microbial siderophores in studies of 1:1 complexes formed with trivalent iron and manganese. However, no data exist concerning DFOB complexes with Co(III), which we hypothesize should be as strong as those with Fe(III) and Mn(III) if the current picture of the ocean biogeochemistry of the three trivalent metals is accurate. We investigated the complexation reaction between DFOB and Co(III) in aqueous solution at seawater pH using base and redox titrations, and then characterized the resulting 1:1 complex Co(III)HDFOB+ using X-ray absorption, resonance Raman spectroscopy, and quantum mechanical structural optimizations. We found that the complex stability constant for Co(III)HDFOB+ (log K [Co(III)HDFOB+] = 37.5 ± 0.4) is in fact five and seven orders of magnitude larger than that for Fe(III)HDFOB+ (log K[Fe(III)HDFOB+] = 32.02) and Mn(III)HDFOB+ (log K[Mn(III)HDFOB+] = 29.9), respectively. Spectroscopic data and the supporting theoretical structural optimizations elucidated the molecular basis for this exceptional stability. Although not definitive, our results nevertheless are consistent with the evolution of siderophores as a response by bacteria to oxygenation, not only because of sharply decreasing concentrations of Fe(III), but also of Co(III).