Rare Oxidation-State Combinations and Unusual Structural Motifs in Hexanuclear Mn Complexes Using 2-Pyridyloximate Ligands

Abstract

The use of phenyl-2-pyridyl ketone oxime and di-2-pyridyl ketone oxime in Mn chemistry has led to hexanuclear clusters with unprecedented (Mn(II)(4)Mn(III)Mn(IV)) or extremely rare (Mn(II)Mn(III)(5) and Mn(II)(3)Mn(III)(3)) metal oxidation-state combinations and uncommon structural motifs.

Crystal structure and magnetic properties of di-copper and di-zinc complexes with di-2-pyridyl ketone oxime

“…Specifically, we started with previously reported chloro derivatives-[Cu 2 (dpko) 2 Cl 4 ]Cl 2 and Zn(dpko)Cl 2 -of transition-metaldpko complexes and synthesized and structurally characterized the corresponding bromo derivatives. In addition, we report the EPR spectroscopic properties of [Cu 2 (dpko) 2 4 ] crystallizes in the space group C2/c, and the cation is structurally similar (Fig. 2) to the previously reported [Cu 2 (dpko) 2 Cl 4 ]Cl 2 [5]; however, the anion is a tetrabromocopper(II)ate instead of a bromide.…”

“…1b). Several reported structures of metal-dpko complexes show multiple metal centers bridged by the dpko ligand [4], and such metal complexes are air-stable under normal conditions.In our efforts to understand the subtle interplay between the steric and electronic factors in the chemistry of these complexes, we studied how replacement of a coordinating ligand with a different ligand affects the three-dimensional and electronic structures at the metal center. Specifically, we started with previously reported chloro derivatives-[Cu 2 (dpko) 2 Cl 4 ]Cl 2 and Zn(dpko)Cl 2 -of transition-metaldpko complexes and synthesized and structurally characterized the corresponding bromo derivatives.…”

“…1b). Several reported structures of metal-dpko complexes show multiple metal centers bridged by the dpko ligand [4], and such metal complexes are air-stable under normal conditions.…”

Oximato-derived metal complexes with triangular and linear magnetic subunits: Synthesis, structure, and magnetism

“…[79] Additionally, the easy self-assembly reactions of phenyl-2-pyridyl ketone oxime and di-2-pyridyl ketone oxime with inorganic Mn II ion have also led to mixed valence hexanuclear clusters with different metal oxidation-state combinations (such as Mn II 4 Mn III Mn IV , Mn II Mn III 5 , and Mn II 3 Mn III 3 ). [10] Undoubtedly, these interesting and ACCEPTED MANUSCRIPT ACCEPTED MANUSCRIPT 4 important findings have greatly advanced the development the metal-oximato chemistry. Herein, to continue the investigations on the magnetostructural relationships along this line, 1-(pyrazin-2-yl)ethanone oxime (mpkoH) was selected as functionally short bridge to react with different paramagnetic ions under controllable conditions.…”

Synthesis and characterization of four novel manganese(II) chains formed by 4,4′-azobis(pyridine) and benzoate or nitrobenzoates: Stabilization of unusual ladder structures

“…As a result, many new systems can be designed in order to explore the important relationship between the different synthetic factors and the structural topologies of the coordination polymers. Among the transition metal ions, manganese-based coordination compounds have received considerable interest in the fields of supramolecular chemistry and crystal engineering not only for their remarkable magnetochemical properties [21][22][23][24], but also for their rich biochemistry [25][26][27]. Furthermore, due to their low cost and toxicity, manganese coordination compounds are growing in importance as homogeneous catalysts [28][29][30][31].…”