Systematic synthesis, structural characterization, and reactivity studies of vanadium(V)–citrate anions [VO2(C6H6O7)]2 2−, isolated from aqueous solutions in the presence of different cations

The aqueous chemistry of vanadium with physiologically relevant ligands constitutes a subject of burgeoning research, extending from bacterial metalloenzymic functions to human-health physiology. Vanadium, in the form of VCl3 and V2O5, reacted expediently with citric acid, in a 1:2 molar ratio in water at pH∼4, and, in the presence of various cations, afforded crystalline materials bearing the general formula (Cat)2[V2O4(C6H6O7)2]·nH2O (A) (Cat+=Na+, NH4 +, n=2; Me4N+, K+, n=4). Exploration of the reactivity of A toward H2O2 yielded the peroxo-containing complexes (Cat)2[V2O2(O2)2(C6H6O7)2]·2H2O (B) (Cat+=K+, NH4 +). Both classes of compounds were characterized analytically and spectroscopically. The X-ray structures of complexes A and B emphasize the exceptional stability of the dimeric rhombic unit VV 2O2, which is retained upon H2O2 reaction, and the preserved mode of coordination of the citrate ligand as a doubly deprotonated moiety. In these complexes, typical six and eight coordination numbers were observed for the Na+ and K+ counter-ions, respectively. The variety of synthetic approaches leading to A, along with the stepwise and direct assembly and isolation of peroxo-compounds (B), denotes the significance of reaction pathways and intermediates in vanadium(III–V)–citrate synthetic chemistry. Hence, a systematic investigation of reactivity modes in aqueous vanadium–citrate systems emerges as a crucial tool for the establishment of chemical interconnectivity among low MW complex species, potentially participating in the intricate biodistribution of that metal ion in biological fluids.