Harnessing scorpionate ligand equilibria for modeling reduced nickel superoxide dismutase intermediates.
Hydrotris(3-phenyl-5-methylpyrazoyl)boratonickel(II) complexes with organoxanthate or dithiocarbamate coligands equilibrate between kappa(2)- and kappa(3)-chelation modes of the scorpionate ligand in solution, connecting N2S2 square-planar and N3S2 pyramidal ligand fields and a spin crossover. The complexes also exhibit quasi-reversible oxidations at low anodic potentials, thus modeling the structure, dynamics, and redox reactivity of the reduced NiSOD active site.
Ma
Huaibo
H
Department of Chemistry and Biochemistry, Ohio University, Athens, Ohio 45701, USA.
Chattopadhyay
Swarup
S
Petersen
Jeffrey L
JL
Jensen
Michael P
MP
D001881:Borates / Q000737:chemistry; D020134:Catalytic Domain; D018360:Crystallography, X-Ray; D008024:Ligands; D008958:Models, Molecular; D009532:Nickel / Q000378:metabolism*; D010084:Oxidation-Reduction; D013482:Superoxide Dismutase / Q000737:chemistry* / Q000378:metabolism*; D017186:Titrimetry
D001881:Borates; D008024:Ligands; D009532:Nickel; D013482:Superoxide Dismutase