Artificial bioinorganic clusters of dinuclear 3d-transition metal ions coordinated by an inorganic coordination ligand.

Artificial bioinorganic clusters of dinuclear 3d-transition metal ions coordinated by an inorganic coordination ligand.
J Inorg Biochem. 2019 Sep 05;201:110821
Authors: Sugiarto, Kawamoto K, Hayashi Y
Abstract
A new biologically relevant cubane-type artificial inorganic ligand was developed to support 3d-transition metal ions of Mn(II), Co(II), Ni(II), Zn(II), Fe(III), and also In(III). All of the reactions produce dinuclear cationic clusters of [({Co(tacn)}2HMo3O13∙H2O){M(H2O)2}]2n+ (M = Mn2+ (4Mn), Co2+ (4Co), Ni2+ (4Ni), Zn2+ (4Zn), n = 2; M = Fe3+ (5), In3+ (6), n = 4), where tacn is the abbreviation of 1,4,7-triazacyclononane ligand. Clusters 4 do not dissolve in any solvents at all to prevent the recrystallization or the further characterization whereas the high solubility of clusters 5 and 6 allowed us to characterize the solution state properties. The dinuclear cores are separated at a fixed-distance in the range of 5.66-5.77 Å for M(II) complexes and 5.45-5.65 Å for M(III) complexes. Each 3d-transition metal ion is supported by two pairs of cis-oxido groups from a cubane unit formed by CoMo3O3(OH) group, and remaining two sites on the 3d-transition metal centers are occupied by two water molecules. The hydroxido group on the cubane unit provides an interaction route through bifurcated hydrogen bondings between dinuclear centers. Three consecutive stepwise reduction waves were observed at -0.73, -0.91,...

Source: Journal of Inorganic Biochemistry - September 4, 2019 Category: Biochemistry Authors: Sugiarto, Kawamoto K, Hayashi Y Tags: J Inorg Biochem Source Type: research