MnO4 as a source of manganese in the direct synthesis of heterobimetallic Cu/Mn complexes

摘要

Complexes [Cu(en)2MnCl4] Solv [en = ethylenediamine, Solv = DMF (1), DMSO (2)], [Cu(phen)2Cl]2- [MnCl4] DMF (3) and [Cu(phen)2Cl]2[Mn(phen)Cl3]Cl 2H2O (4) [phen = 1,10-phenanthroline] have been synthesized by the interaction of copper metal with MnO4 in DMF, DMSO or CH3OH solutions of ethylenediamine or 1,10-phenanthroline. X-ray crystallographic studies of 1 and 2 have shown that the complexes included [Cu(en)2]2+ and [MnCl4]2 building blocks forming zigzag chains, which originate from H-bonding of DMF or DMSO guest molecules. In the crystal structures of 3–4, [Cu(phen)2Cl]+ cations and [MnCl4]2 (3) or [Mn(phen)Cl3] (4) anions form 3D supramolecular frameworks through p–p stacking interactions between phen surfaces, C–H Cl interactions and H-bonding supported by the solvent molecules. The EPR spectra of the polycrystalline compounds 1–3 are different as compared to spectrum for 4 due to the dominant effect of Mn(II) coordination geometry; tetrahedral in the former compounds and square pyramidal in the latter. The hyperfine splitting of frozen solution spectra indicates separation of the Mn(II) and CueenT2t 2 centers under the solvents influence.