AbstractNatural aluminosilicates can contain Fe in tetrahedral or octahedral coordination. Amongst smectites, tetrahedral iron is known to occur in Fe-rich nontronites but few indications exist for the presence of tetrahedral Fe in smectites of the montmorillonite–beidellite series. A set of 38 different bentonites showed a correlation of tetrahedral charge and Fe content in their smectites. All materials with large tetrahedral charge were rich in Fe. This could be explained by a general tendency of Fe to enter the tetrahedral sheet. To investigate this correlation, nine materials were selected and investigated by Mössbauer, UV-Vis, Fe K pre-edge and EXAFS spectroscopy with respect to tetrahedral Fe (Fe[IV]). The latter two methods were at the detection limit but Mössbauer and UV-Vis spectroscopy provided consistent results indicating the significance of both methods in spite of some scatter caused by the overall small amount of tetrahedral Fe. The results indicate the absence of any relation between Fe content and tetrahedral Fe. Tetrahedral Fe can be present in Fe-poor smectites and absent in the case of Fe-rich materials. This means that Fe-rich montmorillonites have a larger tetrahedral charge which is not caused by Fe[IV] but by Al[IV]. A possible explanation for this indirect relation is based on: the coordination of Al3+ in the weathering/smectite-forming solutions determines the coordination in the precipitates; and the Al[IV/VI] ratio increases with increasing pH. The correlation could thus be explained if the pH of weathering solutions generally was higher in Fe-rich parent smectite rocks than in more acidic smectite parent rocks. The relation between tetrahedral charge and Fe content can probably be explained by different geochemical contexts throughout the formation of smectites which affect the coordination of dissolved Al.
Tetrahedral chiral iron(ii) cages with spin crossover behaviors can be almost quantitatively formed by one-pot subcomponent self-assembly with high diastereoselectivity. The cage to cage transformation involving imine exchange was discovered.
The synthesis and structures of four new iron(III) amine-bis(phenolate) complexes are reported. Reaction of anhydrous FeCl3 with the diprotonated tridentate ligand isopropyl-N,N-bis(2-methylene-4-t-butyl-6-methylphenol) (H2L1) and NEt3 produces the trigonal bipyramidal iron(III) complex [NEt3H]+ [FeCl2L1]– (1). The reaction of FeBr3 with the sodium or lithium salts, Na2L1 and Li2L2, results in the formation of FeBr2L1H (2) and FeBr2L2H (3), tetrahedral iron(III) complexes possessing two bromide ligands and quaternized ammonium fragments. A trigonal bipyramidal FeIII hydroxido-bridged dimer, [Fe(μ-OH)L2]2 (4), was also isolated during the synthesis of 3. Single-crystal X-ray molecular structures have been determined for complexes 1–4 and H2L2.
Four new arylamine-acetylene bridged tetrahedral iron and cobalt carbonyl clusters, [Co2(CO)4(μ-CO)2(η2, μ-TMSCCPh)2N 1, [Fe2(CO)6(μ-CO)(η2, μ-TMSCCPh)NH(PhCC TMS)] 2, [(Co2(CO)6(η2, μ-TMSCCPh))33 and [(Fe2(CO)6(μ-CO)(η2, μ-TMSCCPh))2N(Ph CCTMS)] 4, were obtained by reactions of Co2(CO)8and Fe3(CO)12with the bis [4-((trimethylsilyl) ethynyl) phenyamine and tris [4-((trimethylsilyl) ethynyl) phenyamine compounds in suitable solvent, respectively. All clusters are confirmed by C/H elemental analysis, MS,1HNMR and FT-IR spectroscopy. Furthermore, the electrochemical and optical properties of some clusters were also determined by cyclic voltammogram (CV) analysis and UV-Vis spectra.
Hydration of cement with and without fly ash is studied with Mössbauer spectroscopy, XRD, and thermal analysis. Iron in cement is present as Fe3+-ions and occupies two octahedral positions, with close isomer shifts and quadrupole splittings. Iron in fly ash is present as Fe2+and Fe3+, and the Mössbauer spectra display three doublets—two for Fe3+in octahedral coordination and one for Fe2+. A third doublet was registered in the hydrating plain cement pastes after the 5th day, due to Fe3+in tetrahedral coordination in the structure of the newly formed monosulphate aluminate. In cement pastes with fly ash, the doublet of tetrahedral iron is formed earlier because the quantity of ettringite and portlandite is low and more monosulphate crystallizes. No Fe(OH)3phase forms during hydration of C4AF. The fly ash displays pozzolanic properties, which lead to lowering of the portlandite quantity in the cement mixtures and increasing of the high temperature products.
Ferrihydrite is natural ferric oxyhydroxide occurring exclusively nanocrystalline. With ideal formula 5 Fe2 O3 . 9 H2 O, ferrihydrite is quite abundant in sediments, weathering crusts and mine wastes, being characteristic of red pre-soils formed by loose weathered rock plus mineral debris (regoliths) and commonly designated as “2-line” or “6-line” on the basis of the broadened maxima observed in the X-ray diffraction pattern. Synthetic nanocrystalline “6-line” ferrihydrite was recently studied through methods based on atomic-pair distribution functions disclosing the possible occurrence of icosahedral clusters formed by twelve octahedra centred by an inner tetrahedron, all filled by Fe 3+ ions. However, Mössbauer studies were inconclusive about the existence of 4-coordinated iron, thus suggesting that the tetrahedral cation may well be Si4+. In view of such structural uncertainty, a XANES study at the Fe K-edge was undertaken on ferrihydrite from a regolith to ascertain the occurrence of tetrahedral iron. Comparison with data collected from well crystallized iron oxide and hydroxide minerals where Fe 3+/2+ ions occur in octahedral and tetrahedral coordination is described and the results so far obtained are discussed, showing that supplementary study is needed on the elusive structure of ferrihydrite.
Tetrahedral iron featuring an appended Lewis acid: distinct pathways for the reduction of hydroxylamine and hydrazine