High-Valent Manganese in Polyoxotungstates. 3. Dimanganese Complexes of γ-Keggin Anions
- 1 January 1996
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 35 (1) , 30-34
- https://doi.org/10.1021/ic950770p
Abstract
Dimanganese-substituted γ-Keggin heteropoly tungstates have been synthesized by reaction of the lacunary species γ-[(SiO4)W10O32]8- with appropriate mixtures of MnII and MnO4-. The crystal structure of [(CH3)3(C6H5)N]4[(SiO4)W10MnIII2O36H6]·2CH3CN·H2O (anion 1) was determined by X-ray diffraction. Crystallographic data: space group P1̄, a = 12.951(3) Å, b = 14.429(3) Å, c = 20.347(4) Å, α = 81.95(3)°, β = 88.92(3)°, γ = 67.48(3)°, V = 3475.2(13) Å3, and Z = 2. The final R value is 7.29% for 15861 reflections with I > 2σ(I). The anion has the anticipated γ-Keggin structure with virtual C2v symmetry. The two Mn cations occupy adjacent, edge-shared octahedra with bridging hydroxo and terminal aqua ligands. Anion 1 can be oxidized and reduced to the corresponding MnIIIMnIV (2) and MnII2 (3) species respectively. The magnetic susceptibility of 1 between 2 and 300 K indicates that the MnIII cations are antiferromagnetically coupled, with J = −17.0 cm-1 and g = 1.965. No simple magnetic behavior was observed for 2 or 3.Keywords
This publication has 15 references indexed in Scilit:
- A 'smart' catalyst that self-assembles under turnover conditionsNature, 1995
- Bond valence sum analysis of metal-ligand bond lengths in metalloenzymes and model complexesInorganic Chemistry, 1992
- Disubstituted tungstosilicates. 2. .gamma.- and .beta.-isomers of tungstovanadosilicate, [SiV2W10O40]6-: syntheses and structure determinations by tungsten-183, vanadium-51 and silicon-29 NMR spectroscopyInorganic Chemistry, 1991
- Alkene oxidation catalyzed by a ruthenium-substituted heteropolyanion, SiRu(L)W11O39: the mechanism of the periodate-mediated oxidative cleavageJournal of the American Chemical Society, 1990
- Vanadium(V) Substituted DodecatungstophosphatesPublished by Wiley ,1990
- Synthesis and characterization of a bis(oxo)-bridged MN(III)Mn(III) complex, bis(.mu.-oxo)bis[N,N'-bis((6-methylpyrid-2-yl)methyl)ethane-1,2-diamine]dimanganese(III) perchlorateInorganic Chemistry, 1989
- Disubstituted tungstosilicates. 1. Synthesis, stability, and structure of the lacunary precursor polyanion of a tungstosilicate .gamma.-SiW10O368-Inorganic Chemistry, 1986
- Magnetochemistry—Advances in Theory and ExperimentationPublished by Wiley ,1982
- Triheteropolyanions containing copper(II), manganese(II), or manganese(III)Journal of Inorganic and Nuclear Chemistry, 1970
- New fundamental type of inorganic complex: hybrid between heteropoly and conventional coordination complexes. Possibilities for geometrical isomerisms in 11-, 12-, 17-, and 18-heteropoly derivativesJournal of the American Chemical Society, 1970