Metal cluster expansion by addition of low-valent group 4B reagents: crystal and molecular structure of [Os3SnH2(CO)10{CH(SiMe3)2}2]; a compound with hydrogen bridging osmium and tin

Cluster expansion of [Os3H2(CO)10] with [SnR2][R = CH(SiMe3)2] take place in high yield to give [Os3SnH2(CO)10R2], the first closed triosmium–main-group metal cluster to be structurally characterized; a novel feature is the presence of a hydrogen atom bridging the tin atom and one of the osmium atoms.

Synthesis, properties, and X-ray crystal and molecular structures of homoleptic alkenyls of tin and chromium

Reaction of Li(CPhCMe2) with SnCl4 or CrCl3·3thf (thf = tetrahydrofuran) affords the isoleptic compounds Sn(CPhCMe2)4 or [Cr(CPhCMe2)4] respectively. The mode of formation and chemical properties are reported for the chromium species, and the structures of the new compounds, both of which have been determined by single-crystal X-ray analysis, are described.

Alkenyl derivatives of the metals. Oxidative addition to intermediate tin(II) alkenyls; isolation, and crystal and molecular structure of n-butyltris(triphenylethenyl)tin(IV)

Reaction of tin(II) chloride with Li(CPhCPh2) at –78 °C in diethyl ether–hexane–tetrahydrofuran affords a deep red solution whose colour fades on warming, and which we believe contains the (unstable) first dialkenyltin(II) species. The latter survives long enough at low temperatures to undergo intermolecular oxidative addition, and one such adduct leads ultimately to the formation of Sn(CPhCPh2)3Bun, which has been fully characterised including a crystal and molecular structure study. The mechanism of formation of the final product has been examined and results are reported.

Syntheses and crystal structures of [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], two novel heteroleptic tin(II) compounds derived from [Sn-{2-[(Me3Si)2C]C5H4N}Cl], and for [{Sn(C6H2Pri3-2,4,6)2}3] 3, a structural redetermination

Two novel, monomeric heteroleptic tin(II) derivatives, [Sn{2-[(Me3Si)2C]C5H4N}R] [R = C6H2Pri3-2,4,6 1 or CH(PPh2)2 2], have been prepared, characterised by multinuclear NMR spectroscopies and their molecular structures determined by single crystal X-ray diffraction. Both compounds were prepared from the corresponding heteroleptic tin(II) chloro-analogue, [Sn{2-[(Me3Si)2C]C5H4N}Cl], and thus demonstrate the utility of this compound as a precursor to further examples of heteroleptic tin(II) derivatives: such compounds are often unstable with respect to ligand redistribution. In each case, the central tin(II) is three-co-ordinate. Crystals of trimeric [{Sn(C6H2Pri3-2,4,6)2}3] 3 were found to undergo a solid state phase transition, which may be ascribed to ordering of the ligand isopropyl groups. At 220 K the unit cell is orthorhombic, space group Pna21, compared with monoclinic, space group P21/c, for the same crystals at 298 K, in which there is an effective tripling of the now b (originally c) axis. This result illustrates the extreme crowding generated by this bulky aryl ligand.

Synthesis, characterisation, Mössbauer spectra, and structures of some trinuclear iron-tin clusters

Reactions of [Fe3(CO)12] with diaryltin species SnR2(R1= 2,4,6-triisopropylphenyl, R2= 2,6-diethylphenyl, R3= pentamethylphenyl) and with Sn[CH(PPh2)2]2 have been investigated. The tin reagents SnR2(R = R1 or R2) reacted under mild conditions to give in moderate yields the trinuclear species [Fe2(CO)8(µ-SnR12)]1 or [Fe2(CO)8(µ-SnR22)]2, as orange-red crystalline solids, which decompose in air on prolonged exposure. The compound [Fe2(CO)8(µ-SnR42)]3(R4= 2,4,6-triphenylphenyl) can be similarly obtained. Prolonged treatment of the carbonyl with the novel tin reagent SnR32, by contrast, afforded the known compound spiro-[(OC)8Fe2SnFe2(CO)8]4 for which data are briefly reported. Reactions with tin or lead reagents M[CH(PPh2)2]2(M = Sn or Pb) afforded [Fe2(CO)6(µ-CO)(µ-dppm)][dppm = 1,2-bis(diphenylphosphino)methane] rapidly and almost quantitatively. Full crystal and molecular structural data are reported for [Fe2(CO)8(µ-SnR12)] and [Fe2(CO)8(µ-SnR22)]. Mössbauer data are also presented for compounds 1–3, and interpreted in terms of the structural data for these and other systems.

Preparation and magnetic properties of barium ferrites substituted with manganese, cobalt, and tin

Barium ferrites substituted by Mn–Sn, Co–Sn, and Mn–Co–Sn with general formulae BaFe12−2xMnxSnxO19 (x=0.2–1.0), BaFe12−2xCoxSnxO19 (x=0.2–0.8), and BaFe12−2xCox/2Mnx/2SnxO19 (x=0.1–0.6), respectively, have been prepared by a previously reported co-precipitation method. The efficiency of the method was refined by lowering the reaction temperature and shortening the required reaction time, due to which crystallinity improved and the value of saturated magnetization increased as well. Low coercivity temperature coefficients, which are adjustable by doping, were achieved by Mn–Sn and Mn–Co–Sn doping. Synthesis efficiency and the effect of doping are discussed taking into account accumulated data concerning the synthesis and crystal structure of ferrites.

Crystal growth and magnetic properties of tin selenide-doped europium Sn(1-x)Eu(x)Se

The growth and magnetic properties of Tin Selenide (SnSe) doped with Eu(2+) Sn(1-x)Eu(x)Se (x=2.5%) were investigated. Q-band (34 GHz) electron paramagnetic resonance measurements show that the site symmetry of Eu(2+) at 4.2 K is orthorhombic and the Lande factor was determined to be g=1.99 +/- 0.01. The exchange coupling between nearest-neighbor (NN) Eu(2+) ions was estimated from magnetization and magnetic-susceptibility measurements using a model that takes into account the magnetic contributions of single ions, pairs and triplets. The exchange interaction between Eu(2+) nearest neighbors was found to be antiferromagnetic with an estimated average value of J(p)/k(B) =-0.18 +/- 0.03 K. (C) 2009 Elsevier B.V. All rights reserved.

Mineralogy and trace-element geochemistry of the high-grade iron ores of the Aguas Claras Mine and comparison with the Capao Xavier and Tamandua iron ore deposits, Quadrilahero Ferrifero, Brazil

Several major iron deposits occur in the Quadrilatero Ferrifero (QF), southeastern region of Brazil, where metamorphosed and heterogeneously deformed banded iron formation (BIF) of the Caue Formation, regionally called itabirite, was transformed into high- (Fe >64%) and lowgrade (30%ores. Based on their mineralogical composition, three major types of itabirites occur in the QF: siliceous, dolomitic, and amphibolitic itabirite. Unlike other mines in the QF, the Aguas Claras Mine contained mainly high-grade ores hosted within dolomitic itabirite. Two distinct types of high-grade ore occurred at the mine: soft and hard. The soft ore was the most abundant and represented more than 85% of the total ore mined until it was mined out in 2002. Soft and hard ores consist essentially of hematite, occurring as martite, anhedral to granular/tabular hematite and, locally, specularite. Gangue minerals are rare, consisting of dolomite, sericite, chlorite, and apatite in the hard and soft ores, and Mn-oxides and ferrihydrite in the soft ore where they are concentrated within porous bands. Chemical analyses show that hard and soft ores consist almost entirely of Fe(2)O(3), with a higher amount of detrimental impurities, especially MnO, in the soft ore. Both hard and soft ores are depleted in trace elements. The high-grade ores at the Aguas Claras Mine have at least a dual origin, involving hypogene and supergene processes. The occurrence of the hard, massive high-grade ore within ""fresh"" dolomitic itabirite is evidence of its hypogene origin. Despite the contention about the origin of the dolomitic itabirite (if this rock is a carbonate-rich facies of the Caue Formation or a hematite-carbonate precursor of the soft high-grade ore), mineralogical and geochemical features of the soft high-grade ore indicate that it was formed by leaching of dolomite from the dolomitic itabirite by meteoric water. The comparison of the Aguas Claras, Capao Xavier and Tamandua orebodies shows that the original composition of the itabiritic protore plays a major role in the genesis of high- and low-grade soft ores in the QF. Under the same weathering and structural conditions, the dolomitic itabirite is the more favorable to form high-grade deposits than siliceous itabirite. Field relations at the Aguas Claras and Capao Xavier deposits suggest that it is not possible to form huge soft high-grade supergene deposits from siliceous itabirite, unless another control, such as impermeable barriers, had played an important role. The occurrence in the Tamandua Mine of a large, soft, high-grade orebody formed from siliceous itabirite and closely associated with hypogene hard ore suggests that large, soft, high-grade orebodies of the Quadrilatero Ferrifero, which occur within siliceous itabirite, have a hypogene contribution in their formation.

Tratamento superficial DUPLEX com TiN e CrN de aços ferramenta da classe AISI H13 para matrizes de injeção de ligas de alumínio

Este trabalho apresenta um estudo de camada “duplex” em aços para trabalho à quente da classe AISI H13, com enfoque em matrizes de injeção de ligas de alumínio, visando otimizar a vida das matrizes atuando tanto sobre os mecanismos de ataque superficial da matriz pelo alumínio como sobre a formação de trincas por fadiga térmica. O tratamento duplex consistiu em nitretação à plasma, com gás contendo 5% de nitrogênio e diferentes parâmetros de tempos e temperaturas, sendo as amostras posteriormente revestidas com nitreto de titânio (TiN) ou nitreto de cromo (CrN). As camadas nitretadas foram avaliadas através de análises metalográficas, perfis de dureza e difração de raios X, buscando caracterizar e qualificar a camada nitretada. Tendo sido observado na difração de raios X a presença de camada de compostos (nitretos de ferro ε e γ’) mesmo com a utilização de gás pobre em nitrogênio, foram também avaliados substratos nitretados sem a remoção mecânica dos nitretos e com um polimento para remoção destes antes da deposição. A rugosidade dos substratos nitretados com e sem a realização do polimento mecânico também foram determinados, buscando relação deste parâmetro com os resultados obtidos. O conjunto camada nitretada e depósitos (TiN ou CrN) com e sem o polimento mecânico após-nitretação foram avaliados em termos de adesão com ensaios de indentação Rockwell C com análise em microscopia eletrônica de varredura (qualitativamente) e com o teste do risco (quantitativamente) avaliando tanto as cargas críticas para a falha do filme como o modo de falha também em microscopia eletrônica de varredura. Além disso, foram realizados testes de fadiga térmica em banho de alumínio para simulação e avaliação do desempenho da camada “duplex” em condições de trabalho, bem como foram testadas duas condições de nitretação com TiN ou CrN em regime industrial. Os resultados mostram ganhos de adesão crescentes com o aumento dos tempos e das temperaturas de nitretação, além de maiores ganhos com a remoção mecânica (polimento) do substrato nitretado antes da deposição dos filmes. O comportamento, frente às condições de trabalho também foi superior para condições de nitretação com maiores tempos e temperaturas, tanto nos ensaios de laboratório com nos testes em regime industrial.

Morphological evolution of tin oxide nanobelts after phase transition

This article reports a study of the thermal stability and morphological changes in tin oxide nanobelts grown in the orthorhombic SnO phase. The nanobelts were heat-treated in a differential scanning calorimetry (DSC) furnace at 800 degrees C for I It in argon, oxygen, or synthetic air atmospheres. The samples were then characterized by DSC, X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), and high resolution field emission scanning electron microscopy (FE-SEM). The results confirmed that the orthorhombic SnO phase is thermodynamically unstable, causing the belts to transform into the SnO2 phase when heat-treated. During the phase transition, if oxygen is available in the furnace atmosphere, nanofibers grow at the edge of nanobelts at about 50 degrees of the belts' growth direction, while particles grow on the belt surface in the absence of oxygen. Although the decomposition process reduces the nanobelt cell volume by 22%, most belts remain monocrystalline after the heat treatment. The results confirm that phase transition is a decomposition process, which explains the morphological changes in the belts based on metallic tin generated in the process.