Emanuela Schingaro

THE BETTI BASE : ABSOLUTE CONFIGURATION AND ROUTES TO A FAMILY OF RELATED CHIRAL NONRACEMIC BASES

Abstract A detailed protocol for the resolution of the Betti base [i.e. 1-(α-aminobenzyl)-2-naphthol] was investigated and the absolute configuration of the two isomers was established by means of an X-ray diffractometric study. A series of optically active derivatives was also prepared. The list includes the N-benzyl- and the N,N,O-trimethyl derivatives. The N,N-dimethyl derivative was prepared in racemic form by means of the Betti reaction and was resolved into the two enantiomers with an extremely easy and efficient procedure. The O-methyl derivative was prepared in a racemic form and subjected to resolution. The configuration of each base was determined by correlation with the configuration of the Betti amine.

Synthesis and Crystal Structure of Bis(2,3‐dihydro‐3‐methylbenzothiazole‐2‐ylidene)palladium(II) Diiodide: The First Palladium Complex with Benzothiazole Carbene Ligands Suitable for Homogeneous Catalysis

The first diiodo palladium complex with nucleophilic benzothiazole carbenes as ligands has been synthesized and characterized. The complex, which is extraordinarily stable towards heat, oxygen, and moisture, has been found to show good catalytic activity in the Heck coupling reaction.

Crystal chemistry of kimzeyite from Anguillara, Mts. Sabatini, Italy

A single garnet crystal of kimzeyite from Anguillara Sabazia, Sabatini Volcanic District (Rome), has been studied by electron probe microanalysis (EPMA), single crystal X-ray diffraction (XRD) and Raman spectroscopy (RS). X-ray intensities for the structure refinement were collected by means of both a conventional four circle diffractometer (CD) and an area detector (AD) diffractometer. Salient crystallographic data from AD measurements are: a = 12.397(4) A, V = 1905.24 A 3 , μ= 25 cm −1 , crystal dimension ∼ 40 μm, D x =3.83 g cm −3 . The chemical analyses allowed to ascertain that Ca, Ba, Fe, Al, Mg, REE, Zr, Si and Ti are present in the structure. The transition element distribution is: Fe 3+ (Y) ≪ Fe 3+ (Z), and Ti as Ti 4+ occurs only at Y. No hydrogen atoms were detected. The problem of the correct distribution of Ba and REE (essentially Eu and Gd) is dealt with, but not fully solved in the present study. Because of the very small amount of sample available and of the strong dilution of Ba and REE (∼0.03 and 0.02 atoms per formula unit respectively) the correct distribution of these atoms over the X and Y sites is problematical. The radius ratio rule and electrostatic requirements suggest Ba at X and REE at Y. From these principles, the following site distribution can be deduced: Ca 2+ and Ba 2+ at X; Mg 2 +, REE 3+ , Zr 4+ , Ti 4+ , Fe 3+ at Y; Si 4+ , Al 3+ , Fe 3+ at Z. On the other hand, structural details and the best fit between EPMA and XRD site populations indicate REE at X and Ba at Y. Bond strength theory arguments support this hypothesis. The main substitution mechanisms can be summed up as follows: 1) Ti 4+ (Y) + Fe 3+ (Z) ↔ Si 4+ (Z) + M 3+ (Y) [schorlomite substitution]; 2) Zr 4+ (Y) + M 3+ (Z) ↔ Si 4+ (Z) + M 3+ (Y) [kimzeyite substitution]; 3) Mg 2+ (Y) + Zr 4+ (Y) ↔ 2M 3+ (Y) [morimotoite-like substitution], where M 3+ = (Al, Fe). In addition, following the bond strength theory indications, another mechanism which possibly involves the X and Y sites is also taken into account: 4) REE 3+ (X) + Ba 2+ (Y) ↔ Ca 2+ (X) + M 3+ (Y).

Cation-site partitioning in Ti-rich micas from Black Hill (Australia): A multi-technical approach

The crystal chemistry of Ti-rich trioctahedral micas of plutonic origin, cropping out at Black Hill (South Australia) has been investigated by combining electron microprobe analysis, single crystal X-ray diffraction, Mössbauer spectroscopy and X-ray photoelectron spectroscopy. Chemical analyses have shown the samples taken to be quite homogeneous and Ti-rich (TiO2 ≈ 7 wt.%). Mössbauer investigation yielded Fe2+/Fe3+ ≈ 30. X-ray photoelectron spectroscopy analysis seems to suggest the occurrence of three Ti species: octahedral Tr4+(60%), octahedral Ti3+(26%), and tetrahedral Ti4+(14%). The analyzed sample belongs to the 1M polytype and the relevant crystal data from structure analysis are: a = 5.347(1) Å, b = 9.261(2) Å, c = 10.195(2) Å, β = 100.29°(1). Anisotropic structure refinement was performed in space group C2/m, and converged at R = 2.62, Rw = 2.80. Structural details (the c cell parameter, the off-center shift of the M2 cation towards 04, the bond-length distortions of the cis-M2 octahedron, the interlayer sheet thickness, the projection of K−O4 distance along c*, the difference outer-inner) support the occurrence of the Ti-oxy substitution (VIR2+ + 2(OH)− ⇌ Ti4+ + 202− + H2) in the sample. Analysis of structural distortions as a function of the Ti content revealed that the positions of the oxygens 03 and 04 are displaced in opposite senses along [100]. This produces an enlargement of the M1 site with respect to the M2 site and a shortening of the interlayer distance. This trend seems to be in common with other Ti-rich 1M micas of plutonic origin.

Mechanochemical degradation of pentachlorophenol onto birnessite

The existence of a lot of worldwide pentachlorophenol-contaminated sites has induced scientists to concentrate their effort in finding ways to degrade it. Therefore, an effective tool to decompose it from soil mixtures is needed. In this work the efficiency of the phyllomanganate birnessite (KBi) in degrading pentachlorophenol (PCP) through mechanochemical treatments was investigated. To this purpose, a synthesized birnessite and the pollutant were ground together in a high energy mill. The ground KBi-PCP mixtures and the liquid extracts were analyzed to demonstrate that mechanochemical treatments are more efficient in removing PCP than a simple contact between the synthesized birnessite and the pollutant, both in terms of time and extent. The mechanochemically induced PCP degradation mainly occurs through the formation of a surface monodentate inner-sphere complex between the phenolic group of the organic molecules and the structural Mn(IV). This is indicated by the changes induced in birnessite MnO(6) layers as a consequence of the prolonged milling with the pollutant. This mechanism includes the Mn(IV) reduction, the consequent formation of Mn(III) and new vacancies, and free Mn(2+) ions release. The PCP degradation extent is limited by the presence of chloro-substituents on the aromatic ring.

Effect of aging on catalytic properties in mechanochemical degradation of pentachlorophenol by birnessite.

Mechanochemistry, a technique concerning with milling contaminated samples for prolonged times, induces massive degradation of pollutants by grinding them in ball mills with different soil components or additives. In the present study, laboratory experiments were conducted to evaluate the effect of aging on the mechanochemical efficiency of the Mn-oxide birnessite in degrading pentachlorophenol (PCP). A comparative study on an aged birnessite (KBiA), used after 3years from synthesis, and a fresh birnessite (KBiF), employed immediately after synthesis, was carried out. The differences between the two birnessites, evidenced by spectroscopic and diffractometric techniques, are mainly relative to reduction of the Mn(IV) centered at the MnO₆ octahedra layers from the birnessite structure, which represent the most reactive sites for PCP degradation. The long term air drying at room temperature, by favouring reduction of Mn(IV) to Mn(III), produces an inorganic substrate that offers paucity of the less reactive sites for PCP degradation, thus reducing the oxidative potential of the KBiA. Accordingly, the more reactive fresh birnessite was employed in the experiment with a polluted soil. Adding a small amount of KBiF to soil only induces a light increase in PCP removal, probably due to the mechanically induced PCP adsorption and transformation onto clay minerals present in the soil. Besides, adding a higher dose of birnessite causes a stronger degradation of PCP.

XRD, micro-XANES, EMPA, and SIMS investigation on phlogopite single crystals from Mt. Vulture (Italy)

Abstract Selected phlogopite flakes from Mt. Vulture in southern Italy were studied using a combination of single-crystal techniques: electron microprobe analysis (EMPA), secondary ion mass spectrometry (SIMS), single-crystal X-ray diffraction (SCXRD), and micro-X-ray absorption near-edge spectroscopy (XANES). The latter technique was employed to analyze the structure of the Fe-K absorption edge over the region from 7080-8100 eV and to determine Fe3+/∑Fe at a micrometer scale, albeit with large error bars due to known effects of orientation on pre-edge energy. The annite component, Fe/(Mg-i-Fe), of the samples studied ranged from 0.16 to 0.31, the Ti content from 0.11 to 0.27 atoms per formula unit (apfii) and the Ba content from 0.03 to 0.09 apfu. SIMS analysis showed H2O (wt%) = 1.81-3.30, F (wt%) = 0.44-1.29, and Li2O (wt%) = 0.001-0.027. The intra single-crystal chemical variability for major/minor elements (Mg, Fe, Al, Ba, Ti, and K) was found particularly significant for samples VUT191_11 and PG5_1, less significant for the other samples of the set. SIMS data relative to crystals VUT187_24, VUT191_10, VUT191_11, and VUT187_28 showed a noteworthy variation in the concentrations of some light elements (H, Li, and F) with coefficient of variation CV (as 1σ%) up to -18% for H2O. The analyzed micas belong to the 1M polytype. Structure refinements using anisotropic displacement parameters were performed in space group Clim and converged at 3.08 <R < 3.63,3.32 <RW < 3.98%. Micro-XANES results yielded Fe3+/£Fe from 51-93%. Previous Mossbauer data from powdered samples suggested Fe3+/∑Fe values ranging from 49-87%. However, the Fe3+ content determined by both techniques is sometimes remarkably different, in part because of the large errors (±10-15%) presently associated with the micro-XANES technique and m part because the Fe3+ content of a single crystal may significantly depart from the average value obtamed from routine Mossbauer analysis. The combination of EMPA, SIMS, and micro-XANES resulted in the characterization of the samples at a comparable spatial scale. By means of in-situ data and the results of crystallographic investigations, the occurrence of different relative amounts of M3*-oxy [VIM2+ + (OH)- ↔ VIM3+ + O2- + ½H2↑], Ti-oxy substitutions [VIM2+ + 2(OH)- ↔VITi4+ + 2O2- + H2↑], and Ti-vacancy (⃞) substitution (2VIM2+ ↔ + VITi4+ + VI⃞) was ascertained for the studied samples.

An electron microprobe analysis, secondary ion mass spectrometry, and single-crystal X-ray diffraction study of phlogopites from Mt. Vulture, Potenza, Italy: Consideration of cation partitioning

Abstract Mt. Vulture trioctahedral micas-1M mainly consist of phlogopite-annite solid solutions with a minor component of brittle micas. However, both Li-free and Li- and F-rich compositions may coexist in the same volcano-stratigraphic level. We report the results of electron microprobe analysis (EMPA), secondary ion mass spectrometry (SIMS), and single-crystal X-ray diffraction (SCXRD) for three crystals (LC7-27Go, LC7-3Go, and LC7-1R) that are representative of both compositions. EMPA and SIMS showed that sample LC7-1R is richer in TiO2 , Li2O, and F and poorer in H2O than the other samples. Structure refinements using anisotropic displacement parameters for the three samples, performed in space group C2/m, converged at 3.46 ≤ R ≤ 4.34, 3.89 ≤ Rw ≤ 4.39. When considering bond distances, the three samples can be described as homo-octahedral whereas mean atomic numbers suggest that only LC7-1R is meso-octahedral. Significant differences occur among the samples for some distortion parameters commonly used for micas. In particular, LC7-1R displays higher values of BLDM2, shiftM2 and lower values of ΔK-O4 and tK-O4 than those of samples LC7-3Go and LC7-27Go. These differences are ascribed to F- and Ti-substitutions. Cation distributions were obtained by combining EMPA, SIMS, and SCXRD data after analysis of the effect of normalization schemes commonly used in mica formula recalculation. In LC7-3Go and LC7-27Go, Ti is incorporated according to the Ti-Tschermak mechanism, whereas more than one Ti-substitution mechanism occurs in LC7-1R. For the latter sample, octahedral vacancies are present leading to a complex substitution pattern and complex structural distortions related to the special octahedral compositions that were determined.

Crystal chemistry of phlogopite from Vulture-S. Michele Subsynthem volcanic rocks (Mt. Vulture, Italy) and volcanological implications

Abstract Volcanic activity at Mt. Vulture lasted about 750 ka and produced SiO2-undersaturated volcanic rocks that can be classified as old (~700 ka), intermediate (~600-550 ka), and young (~130 ka). The intermediate deposits consist of pyroclastic falls and flows and lavas with compositions ranging from phonolite to foidite. A recent revision of the stratigraphic setting allowed these deposits to be classified into one synthem (the Barile Synthem) and further subdivided into four subsynthems (Toppo S. Paolo, Rionero, Vulture-S. Michele, and Ventaruolo). In the present investigation, trioctahedral micas from sample VUT191 in the Vulture-S. Michele Subsynthem are considered. The host rock has modal diopside (20.2%), analcime (22.8%), plagioclase (27.8%), haüyne (5%), phlogopite (8.9%), and magnetite (6.3%). The micas were studied using chemical (EPMA, C-H-N, SIMS), structural (SCXRD), and spectroscopic (Mössbauer) methods. EPMA of 36 crystals from thin sections and 6 discrete crystals selected for the structural analysis showed remarkable compositional variability, as follows (in wt%): SiO3 = 33.14-38.01, Al2O3 = 15.56-20.45, MgO = 13.02-20.81, FeOtot = 6.34-14.08, TiO2 = 2.34-6.02, K2O = 6.03-9.48, Na2O = 0.50-0.78, and BaO = 0.89-4.06; all crystals proved to be phlogopite. Elemental C-H-N analyses yielded H2O = 2.86 ± 0.36 wt%. The water content was also determined by SIMS on two single crystals, labeled VUT191_2 and VUT191_19, which yielded values of 3.81 ± 0.12 and 1.72 ± 0.08 wt% H2O, respectively. Mössbauer investigation showed that all the iron in VUT191 mica is octahedral with Fe2+ = 25.5% and Fe3+ = 74.5%, confirming that Vulture micas are particularly Fe3+-rich, as also found from previous investigations. Structure refinements using anisotropic displacement parameters were performed in space group C2/m and converged at 1.89 ≤ R ≤ 3.17, 2.09 ≤ Rw ≤ 3.43%. All of the analyzed micas belong to the 1M polytype but exhibit remarkable variations in the c parameter from 10.1569(4) to 10.2458(4) Å. The chemical and structural parameters indicate that the studied micas can be divided into two groups: the first encompassing strongly dehydrogenated micas affected mainly by Ti-oxy [VIM2+ + 2(OH)- ↔ VITi4+ + 2O2- + H2] and M3+-oxy [VIM2+ + (OH)- ↔ VIM3+ + O2- + ½H2, with M3+ = Fe3+, Al3+] substitutions. The second group consist of samples in which vacancy-bearing mechanisms, 2 VIM2+ ↔ VITi4+ + VI□ and 3VIM2+ ↔ 2VIM3+ + VI□ occur.

A crystal chemical insight into sector zoning of a titanian andradite (‘melanite’) crystal

A crystal chemical study was undertaken on a melanite crystal from the pyroclastic deposits of Colli Albani (Lazio, Italy), a Middle-Late Pleistocene volcanic complex belonging to the Roman Perpotassic Province. Previous investigations by electron-probe microanalysis and X-ray topographic methods have shown that melanite from Colli Albani is affected by both sector and concentric zoning. In the present study, we focus on the crystal chemistry of the sector zoning using a combination of Mossbauer spectroscopy, electron probe microanalysis and single crystal X-ray diffraction methods. Electron probe microanalyses show the occurrence of minor chemical differences, especially in the Al and Ti content between non-equivalent {121} trapezohedron and {110} rhombic-dodecahedron growth sectors. Structural analyses are carried out on three crystals fragments taken from the (110), (011) and (121) sectors of the same macrocrystal. We find that the slight chemical difference between the growth sectors produce detectable effects on bond distances: the Y-O distance is significantly shorter and the Z-O distance greater in {121} than in the {110} sector. Two doublets are fitted to both RT and LNT Mossbauer spectra and assigned to octahedral Fe 3+ (∼ 93%) and to dodecahedral Fe 2+ (∼ 7%). As far as the crystal chemical behaviour is concerned, two kinds of heterovalent substitutions seem to affect the melanite structure, i.e. M 2+ (Y) + M 4+ (Y) ⟷ 2M 3+ (Y), morimotoite substitution, with M 2+ = Mg, Mn; M 3+ = Al, Fe; M 4+ = Ti, Zr, and Ti 4+ (Y) + Fe 3+ (Z) ⟷ Si 4+ (Z) + Al 3+ (Y), schorlomite substitution. The former occurs in both growth sectors, {121} and {110}, the latter only in the {121} sector. These results seem consistent with the more rapid growth of {121} sector according to a “layer by layer” mechanism, as revealed by the X-ray topographic investigation.