Complexes Formed in Solution Between Vanadium(IV)/(V) and the Cyclic Dihydroxamic Acid Putrebactin or Linear Suberodihydroxamic Acid

[Image: see text] An aerobic solution prepared from V(IV) and the cyclic dihydroxamic acid putrebactin (pbH(2)) in 1:1 H(2)O/CH(3)OH at pH = 2 turned from blue to orange and gave a signal in the positive ion electrospray ionization mass spectrometry (ESI-MS) at m/z(obs) 437.0 attributed to the monooxoV(V) species [V(V)O(pb)](+) ([C(16)H(26)N(4)O(7)V](+), m/z(calc) 437.3). A solution prepared as above gave a signal in the (51)V NMR spectrum at δ(V )= −443.3 ppm (VOCl(3), δ(V) = 0 ppm) and was electron paramagnetic resonance silent, consistent with the presence of [V(V)O(pb)](+). The formation of [V(V)O(pb)](+) was invariant of [V(IV)]:[pbH(2)] and of pH values over pH = 2–7. In contrast, an aerobic solution prepared from V(IV) and the linear dihydroxamic acid suberodihydroxamic acid (sbhaH(4)) in 1:1 H(2)O/CH(3)OH at pH values of 2, 5, or 7 gave multiple signals in the positive and negative ion ESI-MS, which were assigned to monomeric or dimeric V(V)– or V(IV)–sbhaH(4) complexes or mixed-valence V(V)/(IV)–sbhaH(4) complexes. The complexity of the V-sbhaH(4) system has been attributed to dimerization (2[V(V)O(sbhaH(2))](+) ↔ [(V(V)O)(2)(sbhaH(2))(2)](2+)), deprotonation ([V(V)O(sbhaH(2))](+) – H(+) ↔ [V(V)O(sbhaH)](0)), and oxidation ([V(IV)O(sbhaH(2))](0) –e(–) ↔ [V(V)O(sbhaH(2))](+)) phenomena and could be described as the sum of two pH-dependent vectors, the first comprising the deprotonation of hydroxamate (low pH) to hydroximate (high pH) and the second comprising the oxidation of V(IV) (low pH) to V(V) (high pH). Macrocyclic pbH(2) was preorganized to form [V(V)O(pb)](+), which would provide an entropy-based increase in its thermodynamic stability compared to V(V)–sbhaH(4) complexes. The half-wave potentials from solutions of [V(IV)]:[pbH(2)] (1:1) or [V(IV)]:[sbhaH(4)] (1:2) at pH = 2 were E(1/2) −335 or −352 mV, respectively, which differed from the expected trend (E(1/2) [VO(pb)](+/0) < V(V/IV)–sbhaH(4)). The complex solution speciation of the V(V)/(IV)–sbhaH(4) system prevented the determination of half-wave potentials for single species. The characterization of [V(V)O(pb)](+) expands the small family of documented V–siderophore complexes relevant to understanding V transport and assimilation in the biosphere.