Synthesis and Speciation-Dependent Properties of a Multimetallic Model Complex of NiSOD That Exhibits Unique...

The complex Na₃[{Ni^II(nmp)}₃S₃BTA^alk)] (1) (nmp^2- = deprotonated form of N-(2-mercaptoethyl)picolinamide; H₃S₃BTA^alk = N¹,N³,N⁵-tris(2-mercaptoethyl)benzene-1,3,5-tricarboxamide, where H = dissociable protons), supported by the thiolate-benzenetricarboxamide scaffold (S₃BTA^alk), has been synthesized as a trimetallic model of nickel-containing superoxide dismutase (NiSOD). X-ray absorption spectroscopy (XAS) and ¹H NMR measurements on 1 indicate that the Ni^II centers are square-planar with N₂S₂ coordination, and Ni-N and Ni-S distances of 1.95 and 2.16 Å, respectively. Additional evidence from IR indicates the presence of H-bonds in 1 from the approximately -200 cm^-1 shift in ν_NH from free ligand. The presence of H-bonds allows for speciation that is temperature-, concentration-, and solvent-dependent. In unbuffered water and at low temperature, a dimeric complex (1^A; λ = 410 nm) that aggregates through intermolecular NH···O═C bonds of BTA units is observed. Dissolution of 1 in pH 7.4 buffer or in unbuffered water at temperatures above 50 °C results in monomeric complex (1^M; λ = 367 nm) linked through intramolecular NH···S bonds. DFT computations indicate a low energy barrier between 1^A and 1^M with nearly identical frontier MOs and Ni-ligand metrics. Notably, 1^A and 1^M exhibit remarkable stability in protic solvents such as MeOH and H₂O, in stark contrast to monometallic [Ni^II(nmp)(SR)]^- complexes. The reactivity of 1 with excess O₂, H₂O₂, and O₂^•- is species-dependent. IR and UV-vis reveal that 1^A in MeOH reacts with excess O₂ to yield an S-bound sulfinate, but does not react with O₂^•-. In contrast, 1^M is stable to O₂ in pH 7.4 buffer, but reacts with O₂^•- to yield a putative [Ni^II(nmp)(O₂)]^- complex from release of the BTA-thiolate based on EPR.