ALBERT

Description: The high elevation of the Southern Puna Plateau, the widespread melting of its crust, the gap in intermediate depth seismicity and the recent eruptions of ignimbrite complexes can be explained by delamination of the lithospheric mantle beneath it. To test this hypothesis, an array consisting of 73 broad band and short period seismic stations was deployed in the region for a period of two years starting in 2007. We inverted the data using the two plane wave approach and obtained 1D and 3D Rayleigh wave phase velocities. Our dispersion curve shows that at short periods (〈70 s) the phase velocities are slightly higher than those of the Tibetan plateau and lower than those of the Anatolian plateau. At periods of 100-140 s we observe a low velocity zone that might be remnant hot asthenosphere below a flat slab (7-10 Ma). We estimate the average continental lithosphere thickness for the region to be between 100 and 130 km. Our three dimensional Rayleigh wave phase velocities show a high velocity anomaly at low frequencies (0.007, 0.008 and 0.009 Hz) slightly to the north of Cerro Galan. This would be consistent with the hypothesis of delamination in which a piece of lithosphere has detached and caused upwelling of hot asthenosphere which in turn caused widespread alkaline-collision related volcanism. This interpretation is also corroborated by our shear wave velocity model where a high velocity anomaly beneath the northern edge of Cerro Galan at 130 km depth is interpreted as the delaminated block on top of the subducting Nazca slab.

Description: The reactions of As 2 O 3 , SbCl 3 , and (BiO) 2 CO 3 with oleum (65 % SO 3 ) yielded single crystals of As(S 2 O 7 )(HS 2 O 7 ) [monoclinic, P 2 1 / c , Z = 4, a = 16.549(1), b = 6.6743(5), c = 9.9498(6) Å, β = 102.672(8)°, V = 1072.672(8) Å 3 ], Sb 2 (SO 4 ) 2 (S 2 O 7 ) [monoclinic, P 2 1 / n , Z = 4, a = 9.1586(2), b = 6.9981(2), c = 17.7956(4) Å, β = 100.9690(8)°, V = 1119.73(5) Å 3 ], and Bi 2 (S 2 O 7 ) 3 [triclinic, P , Z = 2, a = 6.5734(1), b = 10.1954(2), c = 11.5121(2) Å, α = 90.996(1)°, β = 96.976(1)°, γ = 94.870(1)°, V = 762.75(2) Å 3 ]. As(S 2 O 7 )(HS 2 O 7 ) shows the arsenic atoms in a trigonal pyramidal coordination of the oxygen atoms of one chelating S 2 O 7 2– and one monodentate HS 2 O 7 – group. The distinct As(S 2 O 7 )(HS 2 O 7 ) molecules are connected with each other by hydrogen bonds to form layers. Sb 2 (SO 4 ) 2 (S 2 O 7 ) shows the Sb 3+ cations in a seesaw-type coordination of oxygen atoms from both anions. In Bi 2 (S 2 O 7 ) 3 the Bi 3+ cations are in a square prismatic oxygen coordination of disulfate units. The antimony and the bismuth compounds exhibit complex three-dimensionally linked structures. The syntheses and the crystal structures, as well as the thermal decomposition of Sb 2 (SO 4 ) 2 (S 2 O 7 ) are presented.

Description: Silver acetate AgOAc reacts with dry liquid ammonia under the formation of colorless needle-shaped crystals of diammine silver(I) acetate [Ag(NH 3 ) 2 ]OAc ( 1 ). The compound crystallizes in the monoclinic space group P 2 1 / c with a = 8.0205(2), b = 12.4161(3), c = 6.0938(2) Å, β = 107.741(4)°, and V = 577.98(3) Å 3 at 123 K with Z = 4. The crystal structure shows the presence of almost linear [Ag(NH 3 ) 2 ] + cations, which are arranged in a corrugated chain of equidistant silver atoms. The Ag–Ag distance is 3.1089(11) Å, which falls in the range of “argentophilic” interactions. After warming to room temperature and removal of the solvent, compound 1 was found unchanged as evidenced by powder X-ray diffraction, thermogravimetric and mass-spectrometric analysis, as well as IR and Raman spectroscopy.

Description: A series of chalcogenidoantimonates, namely [Zn(NH 3 ) 6 ](Sb III 4 S 7 ) ( 1 ), [Zn(NH 3 ) 6 ]{Zn(NH 3 ) 3 Sb V S 4 } 2 · NH 3 ( 2 ), [Mn(NH 3 ) 6 ](Sb III Se 2 ) 2 ( 3 ) and [Zn(NH 3 ) 4 ]{Zn(NH 3 )Sb III Se 3 } 2 · 3NH 3 ( 4 ) are synthesized by solvothermal technique in liquid ammonia at 50 °C from elemental zinc or manganese, antimony and sulfur or selenium. 1 (space group P ) and 2 ( P ) crystallize centrosymmetrically, whereas 3 ( Pna 2 1 ) and 4 ( P 2 1 ) represent polar structures. All compounds contain discrete cationic [Zn(NH 3 ) 4 ] 2+ , [Zn(NH 3 ) 6 ] 2+ , and [Mn(NH 3 ) 6 ] 2+ ammine complexes. In the anionic structure parts, corner-connected trigonal-pyramidal SbS 3 and SbSe 3 are the characteristic building units. 1 and 4 contain 2D polymeric anions, in the latter case with Zn 2+ cations incorporated in a selenidoantimonate(III) network. The polymeric anion in the structure of 3 is a helical chain. 2 is a molecular compound and contains dinuclear anions [S 3 Sb–S–Zn(NH 3 ) 3 ] 2– with Sb V . Raman measurements show the Sb–Ch valence vibrations in the expected region between 250–370 cm –1 for 1 and at 212 cm –1 for 4 . According to the reflectance spectrum 4 is a semiconductor with an optical band gap of 2.05(5) eV.

Description: Chlorine isotope compositions of high-pressure (~2.3 GPa) serpentinite, rodingite, and hydrothermally altered oceanic crust (AOC) differ significantly from high- and ultrahigh-pressure (〉3.2 GPa) metasedimentary rocks in the Aosta region, Italy. Texturally early serpentinites, rodingites, and AOC have bulk δ 37 Cl values indistinguishable from those of modern seafloor analogues (δ 37 Cl = -1.0 to +1.0‰). In contrast, serpentinites and AOC samples that recrystallized during exhumation have low δ 37 Cl values (-2.7 to -0.5‰); 37 Cl depletion correlates with progressive changes in bulk chemistry. HP/UHP metasediments have low δ 37 Cl values (median = -2.5‰) that differ statistically from modern marine sediments (median = -0.6‰). Cl in metasedimentary rocks is concentrated in texturally early minerals, indicating modification of seafloor compositions early in the subduction history. The data constrain fluid sources during both subduction- and exhumation-related phases of fluid-rock interaction: (1) Marine sediments at the top of the downgoing plate likely interacted with isotopically light pore fluids from the accretionary wedge in the early stages of subduction. (2) No pervasive interaction with externally derived fluid occurred during subsequent subduction to the maximum depths of burial. (3) Localized mixing between serpentinites and fluids released by previously isotopically modified metasediments occurred during exhumation in the subduction channel. Most samples, however, preserved protolith signatures during subduction to near-arc depths.

Description: We have measured Ni, Ca, and Mn in olivine phenocrysts from volcanoes in the Galápagos Archipelago to infer the mantle source lithologies. Results show that peridotite is the dominant source lithology for Fernandina, Floreana, Genovesa, Wolf Island, and Darwin Island. These volcanoes largely characterize the PLUME, WD, FLO and DUM Nd, Sr, and Pb isotopic endmembers of Harpp and White (2001). Volcan Wolf, Alcedo, Marchena, and Cerro Azul, also produced from the melting of peridotite sources, have isotopic compositions that can be defined by mixing of the 4 isotopic endmembers. Our analysis suggests that peridotite was present in the sources of the volcanoes covered in this study and therefore is the dominant source lithology of the Galápagos plume. Pyroxenite melting is generally focused in two isotopically distinct domains: Roca Redonda, Volcan Ecuador, and Sierra Negra in the enriched western part of the archipelago, and Santiago, Santa Cruz, and Santa Fe in the depleted east. One implication of this finding is that the Western and Eastern Pyroxenite Domains represent two separate bodies of recycled crust within the Galápagos mantle plume. Furthermore, both isotopically enriched and depleted domains of the archipelago were generated from mixtures of peridotite and pyroxenite. This suggests that there is no relationship between the source lithology of the Galápagos plume and its isotopic characteristics. The identification of peridotite source melting in volcanoes with isotopic characteristics that have been attributed to recycled crust points to the importance of mixing in OIB genesis, consistent with studies in the Canary Islands.

Description: . Sr 2 CoOsO 6 , a new osmium based ordered semiconductor double perovskite was prepared by solid state synthesis from the respective binary oxides. Room temperature PXRD analysis shows the compound to be tetragonal [ I 4/ m ; a = 5.5503(1) Å and c = 7.9320(1) Å], whereas low temperature synchrotron data refinement has revealed a second monoclinic polymorph [ I 2/ m ; a = 5.4969(2) Å, b = 5.4979(2) Å, c = 8.0090(1) Å and γ = 90.527(1)°] with a fully ordered rocksalt arrangement of cobalt and osmium atoms over the perovskite B -sites. Heat capacity and magnetic measurements indicate that Sr 2 CoOsO 6 shows antiferromagnetic ordering below T N = 108 K followed by a second magnetic transition at T 2 = 65 K. It was shown that the change from the tetragonal to the monoclinic phase occurs at T N .

Description: . The ternary germanides RE Rh 6 Ge 4 ( RE = Y, La, Pr, Nd, Sm–Lu) were obtained by arc-melting of the elements and subsequent annealing. Single crystals were grown from bismuth fluxes. The samples were studied by X-ray diffraction on powders. The structures of five members were refined from single crystal diffraction data: LiCo 6 P 4 type, P m 2, a = 715.8(1), c = 387.33(8) pm, wR = 0.0238, 332 F 2 values for LaRh 6 Ge 4 , a = 715.0(1), c = 384.96(7) pm, wR = 0.0211, 329 F 2 values for PrRh 6 Ge 4 , a = 714.28(9), c = 382.57(6) pm, wR = 0.0136, 327 F 2 values for SmRh 6 Ge 4 , a = 714.2(1), c = 381.6(1), wR = 0.0270, 327 F 2 values for GdRh 6 Ge 4 , and a = 714.2(2), c = 379.0(1) pm, wR = 0.0273, 324 F 2 values for HoRh 6 Ge 4 with 19 variables per refinement. The RE Rh 6 Ge 4 structures have two crystallographically independent germanium sites in trigonal prismatic coordination, manifesting the close structural relationship with metal-rich phosphides. Together, the rhodium and germanium atoms build up three-dimensional [Rh 6 Ge 4 ] networks, which leave large channels for the rare earth atoms. Each rare earth atom has coordination number 20 with 12 Rh, 6 Ge, and 2 RE neighbors. Temperature dependent magnetic susceptibility measurements indicate Pauli paramagnetic behavior for YRh 6 Ge 4 , LaRh 6 Ge 4 , and LuRh 6 Ge 4 . The compounds RE Rh 6 Ge 4 ( RE = Gd–Yb) are Curie-Weiss paramagnets. Antiferromagnetic ordering was observed at 8.4(5) K (GdRh 6 Ge 4 ), 13.6(5) K (TbRh 6 Ge 4 ), 5.1(5) K (DyRh 6 Ge 4 ), and 8.9(5) K (YbRh 6 Ge 4 ). DyRh 6 Ge 4 and YbRh 6 Ge 4 show metamagnetic transitions at 2.5(5) and 45(2) kOe, respectively.

Description: Reaction of manganese(II) thiocyanate with 2-chloropyrazine leads always to the formation of a compound of composition Mn(NCS) 2 (2-chloropyrazine) 4 ( 1 - Mn/Cl ) that consists of discrete complexes, in which the manganese cation is coordinated by two terminal thiocyanato anions and four 2-chloropyrazine ligands. In contrast, with 2-methylpyrazine only an aqua complex of composition Mn(NCS) 2 (2-methylpyrazine) 2 (H 2 O) 2 ( 1 - Mn/CH 3 ) is obtained that also consists of discrete octahedrally coordinated complexes. Moreover, a few single crystals of Mn(NCS) 2 (2-chloropyrazine) 4 · Mn(NCS) 2 (2-chloropyrazine) 2 (H 2 O) 2 · 2-chloropyrazine trisolvate ( 2 - Mn/Cl ) and Mn(NCS) 2 (2-methylpyrazine) 2 (H 2 O) 2 · Mn(NCS) 2 (H 2 O) 4 ( 2 - Mn/CH 3 ) were accidently obtained but no larger amounts are available. On heating, 1 - Mn/Cl and 1 - Mn/CH 3 transforms into new compounds of composition Mn(NCS) 2 (L) 2 (L = 2-chloropyrazine) ( 4 - Mn/Cl ) and 2-methylpyrazine ( 3 - Mn/CH 3 ). Surprisingly on further heating 1 - Mn/CH 3 looses additional 2-methylpyrazine ligands and transforms into a new compound of composition Mn(NCS) 2 (2-methylpyrazine) ( 4 - Mn/CH 3 ). Compound 4 - Mn/Cl is isotypic to its cobalt(II) analog and 4 - Mn/CH 3 is isotypic to Cd(NCS) 2 (2-methylpyrazine) reported recently and therefore, both structures were refined by the Rietveld method. The crystal structures of both compounds are strongly related. They consists of dimeric units, in which each two manganese cations are linked by pairs of μ-1,3-bridging thiocyanato anions, which are further connected into layers by single μ-1, 3-bridging anionic ligands. In contrast to 4 - Mn/Cl , in 4 - Mn/CH 3 these layers are further linked into a 3D coordination network by the 2-methylpyrazine ligands. Magnetic measurements reveal that 1 - Mn/Cl , 1 - Mn/CH 3 , and 3 - Mn/CH 3 shows only Curie- or Curie-Weiss paramagnetism, whereas 4 - Mn/Cl and 4 - Mn/CH 3 shows antiferromagnetic ordering at T N = 22.9 K and at 26.5 K. The results of these investigations are compared with those obtained for related compounds.

Description: . Black platelets of Bi 39.67(7) Ru 2 Br 35.0(2) were crystallized from a melt of Bi, BiBr 3 , and Ru. In the tetragonal crystal structure [ P 4/ mbm , a = 1311.92(6) pm, c = 3018.2(4) pm at 155(5) K], cluster cations [(Bi 8 2+ )Ru 2+ (Bi 8 2+ )] are embedded in a matrix of disordered bromido-bismuthate(III) groups. A thorough analysis of the disorder in the anionic part enabled the unambiguous assignment of the cluster charge. The η 4 -coordination of the two Bi 8 2+ square antiprisms to the Ru II atom in the sandwich complex resembles the bonding of Bi 5 + and Bi 8 2+ in the clusters [(Bi 5 + )Ru + (Bi 4 Br 4 )Ru + (Bi 5 + )] and [(Bi 8 2+ )Ru + (Bi 4 Br 4 )Ru + (Bi 5 + )] as well as of Bi 4 2– in 1 ∞ [(Bi 4 2– )Ru + (Bi 4 Br 4 )Ru + ]. By combining crystal chemical considerations for all mentioned compounds and using quantum chemical calculations, a common bonding scheme for the coordination compounds of bismuth polycations and polyanions was established. The η 4 -coordinating bismuth polycations and polyanions act as six electron donors, comparable to nido -carborane ligands, Zintl anions E 9 4– and E 5 6– ( E = Si to Pb), cyclopentadienyl ligands, or the cyclobutadiene dianion. The electron count for the transition metal is 18 in all finite clusters.

Description: . Previous attempts to synthesize and isolate (thiobisphenolate) vanadium(V) dioxido complexes had always provided their dimers containing [O=V(μ-O) 2 V=O] 2+ cores, and these also dominate the solution reactivity. Hence, the behavior of their parent monomers, which represent the major species in solution, has remained uncertain. Herein we report the development of a synthetic route that allowed for the successful isolation, spectroscopic investigation, and structural characterization of the monomer PPh 4 [ S LVO 2 ] ( 3 ) [ S L 2– = 2′2-thiobis(2, 4-di- tert -butylphenolate)]. For this purpose PPh 4 [ S LVOCl 2 ] ( 1 ) had to be accessed first in order to convert it to the ethoxido compound PPh 4 [ S LVO(OEt) 2 ] ( 2 ), which is more prone to hydrolysis. Treatment of 2 with stoichiometric amounts of water followed by immediate cooling to –30 °C led to crystals of 3 . After its dissolution NMR spectra were recorded that were identical with those obtained after dissolution of its dimer, thus confirming the monomer/dimer equilibrium postulated previously. The molecular structure of 3 revealed the absence of a V ··· S interaction, which, however, stabilizes its dimer, and thus suggested the employment of a bisphenolate ligand lacking a bridging sulfur atom to obtain an analogue, which does not undergo dimerization in solution. In Et L 2– the sulfur atom is replaced by an ethylmethine unit and indeed the corresponding complex NBu 4 [ Et LVO 2 ] ( 4 ) proved to be stable as a monomer. Investigation of its potential as a catalyst for the oxidative dehydrogenation of 9-fluorenol confirmed a much lower reactivity in comparison to dimeric complexes, which is discussed.

Description: Two complexes, cis -[MnL 2 (NCS) 2 ] ( 1 ) and cis -[ZnL 2 (NCS) 2 ] ( 2 ) with asymmetrical substituted triazole ligands [L = 3, 4-dimethyl-5-(2-pyridyl)-1, 2, 4-triazole], were synthesized and characterized by elemental analysis, UV/Vis and FT-IR spectroscopy as well as thermogravimetric analyses (TGA), powder XRD, and single-crystal X-ray diffraction. In the complexes, each L molecule adopts a chelating bidentate mode by the nitrogen atoms of pyridyl and triazole. Both complexes have a similar distorted octahedral [ M N 6 ] core ( M = Mn 2+ and Zn 2+ ) with two NCS – ions in the cis position.

Description: Paleomagnetic analysis and radiocarbon dating of an expanded Holocene deep-sea sediment sequence recovered by Integrated Ocean Drilling Program (IODP) Expedition 303 from Labrador Sea Site U1305 (Lat: 57°28.5 N, Long. 48°31.8 W, water depth 3459 m) provides insights into mechanisms that drive both paleomagnetic secular variation (PSV) and magnetization acquisition in deep-sea sediments. Seventeen radiocarbon dates on planktonic foraminifera define postglacial (c. 8 ka) sedimentation rates as ranging from 35 to 〉 90 cm/kyr. Alternating field (AF) demagnetization of u-channel samples show that these homogeneous sediments preserve a strong, stable, and consistently well-defined component magnetization. Normalized remanence records pass reliability criteria for relative paleointensity (RPI) estimates. Assuming that the age of magnetization is most accurately defined by well dated PSV records with the highest sedimentation rates, allows us to estimate and correct for temporal offsets at Site U1305 interpreted to result from post-depositional remanence acquisition at a depth of ~ 20 cm. Comparisons indicate that the northern North Atlantic PSV and RPI records are more consistent with European than North American records, and the evolution of virtual geomagnetic poles (VGP) are temporally and longitudinally similar to global reconstructions, though with much larger latitudinal variation. The largest deviations from a geocentric axial dipole (GAD) are observed during times of the highest intensities, in contrast to the usual assumption. These observations are consistent with the idea that PSV in the North Atlantic and elsewhere during the Holocene results from temporal oscillations of high latitude flux concentrations at a few recurrent locations.

Description: . The multi-shaped amorphous alloy (Ni-B) powders were prepared by complexing reduction route using sodium borohydride (NaBH 4 ) as reductant with assistance of ultrasonic wave. The selected complexants, i.e. water, ammonia, salicylic acid, and ethylene diamine tetraacetic acid (EDTA) possess sequentially escalating complexation ability. The chemical composition and shapes of the product samples obtained under different conditions were characterized by X-ray powder differaction, selected area electron diffraction, and transmission electron microscope. The influence of reaction conditions such as the types of Ni-B, temperatures, NaBH 4 concentrations, and sodium hydroxide (NaOH) content on the hydrogen generation rate of hydrolysis of NaBH 4 solution were investigated in detail. The results show that the as-prepared Ni-B powders all belong to amorphous alloy with variable element contents, and the Ni-B sample prepared from EDTA complexation, possessing the best fineness and dispersity, has the strongest catalytic activity. The mean apparent activation energy of the hydrolysis reaction is 64.90 kJ · mol –1 . The NaBH 4 concentration has little impact on hydrogen generation rate, implying that the catalytic hydrolysis of NaBH 4 solution should be the pseudo zero-order reaction. Keeping the NaOH content at below 5 % could inhibit the hydrolysis of NaBH 4 solution, but the NaOH contents from 10 % to 15 % will significantly promote the hydrolysis rate of NaBH 4 . The hydrolysis reaction mechanisms, especially the effect of NaOH content on the hydrolysis reaction were also analyzed.

Description: The intermetallic compounds Sr 2 Au 6.52 Zn 2.48 , Sr 2 Au 6 Zn 3 , and Sr 2 Au 6 Ga 3 were obtained by induction melting of the elements in sealed tantalum tubes. Their structures were studied by X-ray diffraction on powders and refined from single crystal diffraction data: R c , a = 844.5(2), c = 2187.7(5) pm, wR 2 = 0.0411, 936 F 2 values and 20 variables for Sr 2 Au 6.52 Zn 2.48 ; a = 841.6(2), c = 2191.5(7) pm, wR 2 = 0.0126, 587 F 2 values and 19 variables for Sr 2 Au 6 Zn 3 ; and a = 841.9(2), c = 2191.1(7) pm, wR 2 = 0.0199, 660 F 2 values and 19 variables for Sr 2 Au 6 Ga 3 . The gold substructures of Sr 2 Au 6 Zn 3 and Sr 2 Au 6 Ga 3 can be considered as diamond polytypes with 6R stacking sequences (287–304 pm Au–Au in Sr 2 Au 6 Zn 3 ). The cavities formed by this network are filled in an ordered manner by strontium atoms and Zn 3 (281 pm Zn–Zn), respectively Ga 3 (286 pm Ga–Ga) triangles in a 2:1 ratio. Consequently one can describe the Sr 2 Au 6 Zn 3 and Sr 2 Au 6 Ga 3 structures as ordered substitution variants of the Zintl phase CaIn 2 . This structural relationship is discussed on the basis of a group-subgroup Scheme. Sr 2 Au 6.52 Zn 2.48 shows Zn/Au mixing on the triangle.

Description: The templated borate, [C 9 H 14 N] · [B 5 O 6 (OH) 4 ], was synthesized under hydrothermal conditions. Single crystal X-ray diffraction techonology reveals that it crystallizes in the triclinic system, space group P (No. 2). The material was also characterized by element analysis, Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction (PXRD), thermogravimetric and differential thermal analysis (TG-DTA), and luminescence spectroscopy. The compound consisted of isolated pentaborate [B 5 O 6 (OH) 4 ] – and N -butylpyridinium cations [C 9 H 14 N] + . The [B 5 O 6 (OH) 4 ] – anions are connected together by hydrogen bonds to form a three-dimensional framework, in which [C 9 H 14 N] + cations are located in. [C 9 H 14 N] · [B 5 O 6 (OH) 4 ] exhibits tunable luminescence emission at 415–458 nm by means of heating treatment from 100 to 300 °C.

Description: Two alkylimido derivatives of hexamolybdate, (Bu 4 N) 2 [Mo 6 O 18 (≡N- o -COOCH 3 C 6 H 4 )] ( 1 ) and (Bu 4 N) 2 [Mo 6 O 18 (≡N- o -COOCH 2 CH 3 C 6 H 4 )] ( 2 ), were synthesized in high purity and good yields by the reaction of [(C 4 H 9 ) 4 N] 4 [α-Mo 8 O 26 ] and methyl anthranilate or ethyl- o -aminobenzoate hydrochloride with N , N ′-dicyclohexylcarbodiimide (DCC) as a dehydrating agent in dry acetonitrile solution, which were characterized by elemental analyses, IR, UV/Vis, and 1 H NMR spectroscopy as well as ESI-MS, and single-crystal X-ray diffraction study. Compound 1 crystallizes in the monoclinic space group P 2 1 / n with one-dimensional chain structure via intramolecular hydrogen bond. Compound 2 also crystallizes in the monoclinic space group P 2 1 / n with dimer structure by intramolecular hydrogen bonds and π–π interactions between the pairs of cluster anions.

Description: The cover picture shows the frontispieces of all articles published in this Special Issue with research reports from DFG priority program 1178 “Experimental Electron Density as Key to Understanding Chemical Interactions”, highlighting the diverse range of chemistry that is covered herein. Biological processes that determine the effects of drugs consist on a certain interaction between agent and receptor. This molecular recognition is influenced by the electron density distribution. Analysis of these processes enables the rational synthesis of drugs. Electron density measurements are moreover significant for the design of advanced materials with specific features, e.g. the development of new pigments. Thus, color, stability, and durability can be tuned by modifying the electron density. Selected substance classes used in chemical synthesis, drug design and material science were analyzed and their binding and recognition processes were studied and quantified by means of electron density measurements.

Description: The conditions permitting mantle serpentinization during continental rifting are explored within 2D thermotectonostratigraphic basin models, which track the rheological evolution of the continental crust, account for sediment blanketing effects, and allow for kinetically controlled mantle serpentinization processes. The basic idea is that the entire extending continental crust has to be brittle for crustal scale faulting and mantle serpentinization to occur [ Perez-Gussinye and Reston , 2001]. The isostatic and latent heat effects of the reaction are fully coupled to the structural and thermal solutions. A systematic parameter study shows that a critical stretching factor exists for which complete crustal embrittlement and serpentinization occurs. Increased sedimentation rates shift this critical stretching factor to higher values as sediment blanketing effects result in higher crustal temperatures. Sediment supply has therefore, through the temperature-dependence of the viscous flow laws, strong control on crustal strength and mantle serpentinization reactions are only likely when sedimentation rates are low and stretching factors high. In a case study for the Norwegian margin we test whether the inner lower crustal bodies (LCB) imaged beneath the Møre and Vøring margin could be serpentinized mantle. Multiple 2D transects have been reconstructed through the 3D data set by Scheck-Wenderoth and Maystrenko [2011]. We find that serpentinization reactions are possible and likely during the Jurassic rift phase. Predicted thicknesses and locations of partially serpentinized mantle rocks fit to information on LCBs from seismic and gravity data. We conclude that some of the inner LCBs beneath the Norwegian margin may be partially serpentinized mantle.

Description: . Reactions of the coordinatively unsaturated complexes [Fe 2 (μ-P R 2 )(μ-P R ′ 2 )(CO) 5 ] [ R = R ′ = t Bu ( 1 ); R = t Bu, R ′ = Cy ( 2 )] with nitric oxide in toluene at elevated temperatures were investigated. Thus, the new complexes [Fe 2 (μ-P t Bu 2 ) 2 (NO) 4 ] ( 3 ) and [Fe 2 (μ-P t Bu 2 )(μ-PCy 2 )(NO) 4 ] ( 4 ) were obtained in good yields. The molecular structure of 3 was confirmed by X-ray diffraction study. Compound 4 was also prepared from the coordinatively saturated species [Fe 2 (μ-P t Bu 2 )(μ-PCy 2 )(CO) 6 ] ( 2a ) with nitric oxide in refluxing toluene. Further closely related reactions at 60 °C with the complex 1 and [FeRu(μ-P t Bu 2 ) 2 (CO) 5 ] ( 5 ), respectively, were investigated using preliminary crystal structure determination results.

Description: Two new materials of the composition ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CoBr 4 ] 2– ( 1 ) and ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CuBr 4 ] 2– ( 2 and 3 ), of which the latter exists in two polymorphs, were synthesized. The materials display the synthetically targeted structures, comprising of layers of complex metal ions and layers of long-chain sulfonium cations. The crystal structures of the materials were determined. The interlayer distances are around 24 Å, with metal–metal distances about 8 Å. The magnetic properties of 1 were investigated, and the material is paramagnetic. ({CH 3 (CH 2 ) 15 (CH 3 ) 2 S} + ) 2 [CuBr 4 ] 2 is polymorphic. Both polymorphs crystallize with triclinic symmetry.

Description: The origin of the Bermuda swell and volcanism remains enigmatic. The lack of an associated time-progressive hotspot track and absence of present-day volcanic activity make it difficult to reconcile with a deep mantle plume model. We analyze shear wave splitting measurements to estimate mantle flow direction and receiver function stacks to place constraints on the mantle transition zone thermal structure. *KS phases exhibit well-resolved null arrivals (no splitting) beneath the swell over a range of back azimuths. We find that the 410 and 660 km discontinuities are 49 ± 5 km and 19 ± 5 km deeper than the global average, respectively, leading to a transition zone thickness that is 27 ± 4 km thinner than average. Together, an apparently isotropic upper mantle and a thinned mantle transition zone suggest that mantle flow is primarily vertical beneath the swell, consistent with the presence of hot, buoyant mantle at depth.

Description: Single crystals of Rb 2 H 2 P 2 O 6 · 2H 2 O could be obtained from aqueous solutions of hypodiphosphoric acid and rubidium carbonate. Its crystal structure was determined by X-ray diffraction and it crystallizes in the monoclinic space group P 2 1 / c with Z = 4. The salt-like title compound consists of [H 2 P 2 O 6 ] 2– units in staggered P 2 O 6 -skeleton conformation, Rb + cations, and H 2 O molecules, held together by intermolecular hydrogen bonds of the type O ··· O. The vibrational spectra (IR/FIR and Raman) of the rubidium salt were recorded and an assignment of the vibrational modes is proposed based on the point group C 2 h for the P 2 O 6 -skeleton of the anion. The thermal behavior of Rb 2 H 2 P 2 O 6 · 2H 2 O is dominated by a complex TG decay indicating a simultaneous H 2 O delivery coupled with a disproportionation of [H 2 P 2 O 6 ] 2– , what is also supported by Raman spectra of heated samples.

Description: Three metal coordination polymers {[Co(L) 2 (H 2 O) 2 ] 2+ · 2NO 3 – } n ( 1 ), {[Mn(L) 2 (H 2 O) 2 ] 2+ · 2Cl – · 3H 2 O} n ( 2 ), and [ZnL(ba) 2 ] n ( 3 ) [L = 3, 5-bis(imidazole-1-yl)pyridine and Hba = benzoic acid] were synthesized and structurally characterized by IR spectroscopy, elemental analysis, X-ray powder diffraction, and X-ray single crystal diffraction. Complex 1 shows a one-dimensional (1D) chain structure. Adjacent chains are connected by hydrogen bonding and nitrate groups to form a 3D network. Complex 2 features a 2D layer structure. A three-dimensional network is constructed through the cluster consisting of two chloride ions and three water molecules. Complex 3 shows a 1D zigzag chain structure that further twists together to form a 3D network. The X-ray powder diffraction patterns were compared with the simulated ones. Moreover, the luminescent properties of 1 – 3 were investigated in the solid state at room temperature, and the thermogravimetric analyses were carried out to study the thermal stability of the three complexes.

Description: . The reactions of FeCl 3 · 6H 2 O and 2-(2′-hydroxyphenyl)-2-thiazoline as a bidentate O-N donor thiazoline ligand (thoz) afford a five-coordinate Fe III complex [Fe(thoz) 2 Cl] with a distorted square pyramidal configuration. Complex [Fe(thoz) 2 Cl] was isolated as air-stable crystalline solids and fully characterized, including by single-crystal X-ray structure analysis. Complex [Fe(thoz) 2 Cl] shows very efficient reactivity in the oxidation of sulfides to their corresponding sulfoxides using urea hydrogen peroxide (UHP) as the oxidant at room temperature in air.

Description: Two copper(I) complexes of compositions [Cu(HL)I] 2 · EtOH ( 1 ) and [Cu(HL) 3 ]I · MeOH ( 2 ) were synthesized via the reactions of HL [HL = 2(4, 5-diphenyl-1 H -imidazol-2-yl)pyridine] and CuI in EtOH and MeOH, respectively, under solvothermal conditions. The complexes were characterized by X-ray single crystal diffraction, IR spectroscopy, and elemental analysis. Compounds 1 and 2 are catalytically active towards ketalization reaction, giving various ketals under mild conditions.

Description: Mineral samples from the Prasolovskoe epithermal Au-Ag deposit, Russia, were investigated via transmission electron microscopy (TEM). One component was identified as the mineral kurilite Ag 8 Te 3 Se according to the data obtained from electron diffraction (ED) and Fourier transform analyses of high resolution micrographs. Micrometer-sized grains of kurilite were found next to other noble metal chalcogenide domains like the hessite-type. The EDX microprobe analyses of the kurilite domains were determined with the chemical composition Ag 7.9 Au 0.1 Te 2.9 Se 1.0 which is consistent with kurilite doped by gold. Additionally noble metal polychalcogenidehalides (NMPH) were identified via ED. Monoclinic and tetragonal polymorphs of Ag 5 Te 2 Cl were observed for the first time in a mineral sample. One additional component, whose composition equates the kurilite-type component with regard to Ag, Au, Te, and Se but with a marginal chlorine component, crystallizes in a structure type known from synthetic NMPH, namely Ag 23 Te 12 X (X = Cl, Br). This phase as well as the phases Ag 10 Te 4 Br 3 and Ag 20 Te 10 Br 2 was found next to each other in an also investigated synthetic sample.

Description: We present an improved density model and a new structural map of the Neapolitan Yellow Tuff caldera, the active portion of the nested Campi Flegrei caldera. The model was built using a new 3D inversion of the available high-precision gravity data, and a new digital terrain and marine model. The inversion procedure, based on a variable-depth lumped assembling of the subsurface gravity distribution via cell aggregation, gives better defined insights into the internal caldera architecture, that well agree with the available geological, geophysical and geochemical data. The adopted 3D gravity method is highly efficient for characterizing the shallow caldera structure (down to 3 km depth) and defining features related to regional or volcano tectonic lineaments and dynamics. In particular, the resulting density distribution highlights a pronounced density low in correspondence of the central portion of the caldera with a detail not available till now. The joint interpretation of the available data, suggests a subsurface structural setting that supports a piecemeal collapse of the caldera, and allows the identification of its headwall. Positive gravity anomalies localize dense intrusions (presently covered by late volcanic deposits) along the caldera marginal faults, and the main structural lineaments both bordering the resurgent block and cutting the caldera floor. These results allow us to both refine the current geological-structural framework and propose a new structural map that highlights the caldera boundary and its internal setting. This map is useful to interpret the phenomena occurring during unrest, and to improve both short- and long-term volcanic hazards assessment.

Description: Catastrophic collapses of submarine volcanoes have the potential to generate major tsunami, threatening many coastal populations. Recognizing the difficulties surrounding anticipations of these events, quantitative assessment of collapse-prone regions based on detailed morphological, geological and geophysical mapping can still provide important information about the hazards associated with these collapses. Rumble III is one of the shallowest, and largest, submarine volcanoes found along the Kermadec arc, and is both volcanically and hydrothermally active. Previous surveys have delineated major collapse features at Rumble III; based on time-lapse bathymetry, dramatic changes in the volcano morphology have been shown to have occurred over the interval 2007 to 2009. Furthermore, this volcano is located just ˜300 km from the east coast of the North Island of New Zealand. Here, we present a geophysical model for Rumble III, that provides the locations and sizes of potential weak regions of this volcano. Shipborne and near-seafloor geological and geophysical data collected by the AUV Sentry are used to determine the subsurface distribution of weak and unstable volcanic rocks. The resulting model provides evidence for potentially unstable areas located in the Southeastern flank of this volcano which should be included in future hazard predictions.

Description: Broadband seismic experiments over the last two decades have produced dense data coverage across Tibet. Yet, the mechanism of the India-Asia lithospheric convergence beneath it remains a puzzle, with even its basic features debated and with very different end-member models advocated today. We measured highly accurate Rayleigh- and Love-wave phase-velocity curves in broad period ranges (up to 5-200 s) for a few tens of pairs and groups of stations across Tibet, combining, in each case, hundreds to thousands of inter-station measurements made with cross-correlation and waveform-inversion methods. Robust shear-velocity profiles were then determined by extensive series of non-linear inversions of the data, designed to constrain the depth-dependent ranges of isotropic-average shear speeds and radial anisotropy. Temperature anomalies in the upper mantle were estimated from shear velocities using accurate petro-physical relationships. Our results reveal strong heterogeneity in the upper mantle beneath Tibet. Very large high-velocity anomalies in the upper mantle are consistent with the presence of underthrust (beneath southwestern Tibet) and subducted (beneath central and eastern Tibet) Indian lithosphere. The lithosphere. In contrast to the Indian lithosphere, Tibetan lithosphere and asthenosphere display low to normal shear speeds; Tibetan lithosphere is thus warm and thin. Radial anisotropy in the upper mantle is weak in central and strong in northeastern Tibet, possibly reflecting asthenospheric flow above the subducting Indian lithospheric slab.

Description: The Pacific Northwest (PNW) has experienced voluminous intraplate volcanism over the past ~17 Ma, beginning with the Steens/Columbia River flood basalts and continuing with the still-ongoing volcanism in the High Lava Plains (HLP) and eastern Snake River Plain (SRP). Here we present two complementary datasets (SKS splitting and Rayleigh wave phase velocity anisotropy) that place constraints on the anisotropic structure of the upper mantle beneath the HLP and SRP regions. Beneath the HLP, SKS phases reveal dominantly E-W fast splitting directions and large (up to ~2.7 sec) delay times, with pronounced lateral variations in δ t . Lateral and depth variability in the strength of anisotropy beneath the HLP is also evident from Rayleigh wave dispersion. Beneath the SRP, SKS splitting delay times are much smaller (~0.5 sec) and surface wave observations suggest a region of upper mantle anisotropy (~50-150 km depth) with a geometry that deviates significantly from the generally plate motion parallel fast directions observed just outside of the SRP. Beneath the HLP, the geometry of the anomalously strong anisotropy is similar to the anisotropy in the deeper parts of the upper mantle, resulting in constructive interference and large SKS splitting delay times. Beneath the SRP, the geometry of the anomalous anisotropic region in the shallow mantle is different, resulting in destructive interference and reduced SKS splitting delay times. We discuss several possible explanations for these observations, including variations in olivine lattice preferred orientation (LPO) strength, transitions in olivine fabric type, and a contribution from aligned partial melt.

Description: Eight chelating resins were synthesized in high yields by supporting 2-aminomethylpyridine, 2, 2′-dipyridylamine, 1, 2-phenylenediamine and 1, 2-ethylenediamine on Merrifield and Wang resins, respectively. These resins were used both as support of reducing complexes and as alkali metal sensors. 16 stable and easy to prepare reducing complexes, derived from the chelating resins and LiBH 4 and NaBH 4 , were prepared in good yields. These complexes showed chemoselectivity to reduce aldehydes in a low molar ratio and short time reactions. The fluorescence-sensing behavior of the chelating resins for alkali metal was studied. The fluorescence response of the materials where 1, 2-phenylenediamine is supported on Merrifield and Wang resins indicate that they behave as sensors for Li + and K + , respectively.

Description: The reaction of Fe 3 (CO) 12 with (C 3 H 5 ) 2 NCS 2 K in THF at room temperature afforded a red-brown solution. Treatment of the thus-obtained solution with MeI and PhCH 2 Br afforded clusters 1 , (μ-MeS)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ), and 2 , (μ-PhCH 2 CO)Fe 2 (CO) 6 (μ 4 -S)Fe 2 (CO) 6 (μ-CN(C 3 H 5 ) 2 ). Their structures were unambiguously determined by X-ray crystallography. Therefore, this methodology provides a novel route for the syntheses of spiro-S Fe/S clusters with aminocarbyne ligands.

Description: This study presents the preparation of 5-azido-3-nitro-1 H -1,2,4-triazole ( 1 ) in both good yield and high purity, starting from commercially available chemicals in a three step synthesis. Furthermore, several metal and nitrogen-rich salts with sodium ( 3 ), potassium ( 4 ), cesium ( 5 ), silver ( 6 ), lead ( 7 ), ammonium ( 8 ), guanidinium ( 9 ), and aminoguanidinium ( 10 ) were prepared by simple acid-base reactions. All compounds were well characterized by various means, including vibrational (IR, Raman) and multinuclear ( 1 H, 13 C, 14 N, 15 N) NMR spectroscopy, mass spectrometry, and DSC. Additionally the structure of 7 was determined by single-crystal X-ray diffraction. The sensitivities towards various outer stimuli (impact, friction, electrostatic discharge) were determined according to BAM standards. The metal salts were tested as potential primary explosives utilizing various preliminary tests.

Description: With Sharpless' and Meldal's discovery of the immensely supportive effect that metal catalysis has on Huisgen's classical 1,3-dipolar cycloaddition, azides (RN 3 ) – long underappreciated in organic synthesis – suddenly got in the focus of attention as most crucial players in sensational ‘click chemistry'. Less noisy though with the same commitment and even a much broader scope of scientific topics and objectives, the inorganic azide chemistry has made just as great strides in the last few decades. This review (Part I) gives an introductory survey of the most important results, and informs about modern developments and general trends. Particular emphasis is placed on the recent successful approaches to highly unstable homoleptic azido metal complexes of the main group and early transition elements, as well as on the enormous structural versatility caused by the ‘flexidentate' N 3 – ligand with its unsurpassed bridging capacities. The presentation in this paper of selected compounds and reactions is meant, in a way, as a prelude to the [3+2]-cycloadditions of metal azides and related species which will be covered in-depths in Part II. A large part of the comments finally deals with applications in fields such as catalysis, high explosive performance or magnetism of metal compounds containing azide, today certainly one of the most attractive research areas world-wide.

Description: The long-chain ligand, 1-phenyl-3-methyl-4-heptanoyl-pyrazol-5-one (HL) and its zinc(II) complex ZnL 2 were synthesized. The structure and the properties of ZnL 2 were characterized by elemental analysis, IR spectroscopy, X-ray diffraction, and thermogravimetric analysis. The zinc ion is five-coordinated in a square-pyramidal environment by four oxygen atoms of the HL ligands in the equatorial plane and one water molecule in the axial position. The water molecule is directly bonded to Zn 2+ and involved in intermolecular hydrogen bonding network. The complex and its corresponding ligand were screened in vitro against some strains of the human pathogenic bacteria. The metal complex exhibits higher antibacterial activity than its corresponding ligand. The complex exhibits purple effect emission as the result of fluorescence from the intraligand emission excited state.

Description: The microporous metal-organic framework Cd 2 (ABTC)(H 2 O)(DMA) 2 · H 2 O · 3DMA ( 1 ) (H 4 ABTC = 3,3′,5,5′-azobenzenetetracarboxylic acid; DMA = N , N ′-dimethylacetamide) was prepared by solvothermal reaction and characterized. X-ray structure analysis revealed that compound 1 is a three-dimensional (3D) open framework with 2D channels. The topology is based on a PtS net, constructed of 4-connected rectangular ABTC 4– units with 4-connected tetrahedral dinuclear Cd 2 (CO 2 ) 4 (H 2 O)(DMA) 2 secondary building units (SBUs). The solid-state excitation-emission spectra showed that the strongest emission peak is at 403 nm upon excitation at λ = 287 nm.

Description: The bulk composition of the silicate portion of the Earth (BSE) has long been assumed to be tied to chondrites, in which refractory, lithophile elements like Sm and Nd exist in chondritic relative abundances. However, the 142 Nd/ 144 Nd ratios of modern terrestrial samples are 18±5 ppm higher than the ordinary-chondrite reservoir, and this challenges the traditional BSE model. Here we investigate a hypothesis that this terrestrial 142 Nd excess is related to a Sm/Nd ratio 6% higher than chondritic. This Sm/Nd ratio yields a superchondritic 143 Nd/ 144 Nd (~0.5130) similar to that identified in the highest 3 He/ 4 He mantle reservoir, and we argue that this reservoir represents the BSE composition for lithophile elements. We develop a compositional model for BSE in which the elevated Sm/Nd requires a shift of 143 Nd/ 144 Nd from 0.51263 (chondritic) to 0.51300. The new BSE composition is depleted in highly incompatible elements, including K, relative to the chondrite-based BSE, and offers a solution the “missing” 40 Ar paradox. This BSE compositional model requires that 〉83% of the mantle is depleted to form continental crust. It also implies a ~30% reduction in BSE U, Th and K, and therefore in the current rate of radiogenic heating and, thus, a proportional increase in the heat flow delivered to surface by plate tectonics. We explore thermal history models including effects related to a newly recognized evolution in the style of plate tectonics over Earth history: The lower radiogenic heat production may delay the onset of core convection and dynamo action to as late as 3.5 Gyr.

Description: P(2-SHC 6 H 4 ) 3 ( PS 3 H 3 ) reacts with GaMe 3 (1:1) to give GaMe{P(2-SC 6 H 4 ) 2 (2-SHC 6 H 4 )-κ 3 S , S′,P } ( 1 ), which could be deprotonated with NEt 3 to give [NEt 3 H][GaMe{P(2-SC 6 H 4 ) 3 -κ 3 S , S′,P }] ( 2 ). The 1:2 reaction of E (2-SHC 6 H 4 ) 3 [ E = P ( PS 3 H 3 ), As ( AsS 3 H 3 )] with GaMe 3 gave the dinuclear complexes GaMe{ E (2-SC 6 H 4 ) 2 (2-S{GaMe 2 (THF)}C 6 H 4 )-κ 3 S , S′,E } [ E = P ( 3 ), As ( 4 )]. Serendipitous hydrolysis of 4 resulted in small amounts of the hexanuclear gallium hydroxide complex cyclo -{GaMe(μ-OH)} 6 {As(2-SC 6 H 4 ) 3 -κ S , S′,S′′ } 2 ( 5 ). Complexes 1 – 4 were fully characterized, complexes 2 – 5 also by X-ray crystallography.

Description: Topological aspects of the experimental electron density in TiB 2 reconstructed on base of the multipole model are obtained from high-resolution single-crystal X-ray diffraction data. The features of electron density are compared with quantum chemical calculations and analysed in terms of Quantum Theory of Atoms in Molecules for the interpretation of atomic interactions. In spite of some differences in the Laplacian, both experimental and calculated density confirmed two main bonding interactions. The B–B bond critical point suggests a shared-type interaction with pronounced ellipticity in the boron layer, whereas B–Ti bond critical point reveals an interaction intermediate between shared and closed-shell type. Both, theory and experiment indicate a non-structured spherical topology in the penultimate shell of Ti. Integration of the electron density over the atomic basins reveals a charge transfer of 1.1 e (experiment) and 1.4 e (theory) from titanium to boron network, respectively.

Description: The internal geological structure of the Northeast German Basin (NEGB) is affected by intense salt diapirism and by the presence of several stratified aquifer complexes of regional relevance. The shallow Quaternary to late Tertiary freshwater aquifer is separated from the underlying Mesozoic saline aquifers by an embedded Tertiary clay enriched aquitard (Rupelian Aquitard). An important feature of this aquitard is that hydraulic connections between the upper and lower aquifers do exist in areas where the Rupelian Aquitard is missing (hydrogeological windows). Three-dimensional thermohaline numerical simulations are carried out to investigate the effects of such hydrogeological windows in the Rupelian Aquitard on the resulting groundwater, temperature and salinity distributions. Numerical results suggest that hydrogeological windows act as preferential domains of hydraulic interconnectivity between the different aquifers at depth, and enable vigorous heat and mass transport which causes a mixing of warm and saline groundwater with cold and less saline groundwater within both aquifers. In areas where the Rupelian Aquitard confines the Mesozoic aquifer, dissolved solutes from major salt structures are transported laterally giving rise to plumes of variable salinity content ranging from few hundreds of meters to several tens of kilometers. Furthermore, destabilizing thermal buoyancy forces may overwhelm counteracting stabilizing salinity induced forces offside of salt domes. This may result in buoyant upward groundwater flow transporting heat and mass to shallower levels within the same Mesozoic Aquifer.

Description: The stannides Li 2 CuSn 2 and Li 2 AgSn 2 were synthesized by induction-melting (or in a muffle furnace) of the elements in sealed niobium ampoules. The new phases were characterized by powder X-ray diffraction. The structures of both stannides were investigated by X-ray diffraction on single crystals: Li 2 AuSn 2 type, I 4 1 / amd , a = 442.6(1), c = 1940.9(8) pm, wR 2 = 0.0742, 310 F 2 values for Li 2 CuSn 2 and a = 456.33(9) c = 2018.2(6) pm, wR 2 = 0.0626, 339 F 2 values for Li 2 AgSn 2 with 10 variables for each refinement. The transition metal ( T ) atoms have tetrahedral tin coordination. The T Sn 4 tetrahedra are condensed via common corners forming layers that are further condensed by Sn–Sn bonding, leading to three-dimensional [CuSn 2 ] and [AgSn 2 ] networks which leave distorted hexagonal channels for the lithium atoms. The lithium ions show considerable mobility, with activation energies of 0.29 and 0.47 eV extracted from variable temperature 7 Li solid state NMR spectra. 119 Sn Mössbauer spectra at 78 K show signals at isomer shifts of δ = 2.13(1) mm s –1 for Li 2 CuSn 2 and δ = 2.07(1) mm s –1 for Li 2 AgSn 2 . The signals show electric quadrupolar splitting because of the non spherical environment of the tin nuclei. A minor impurity of β-Sn could be identified in both spectra.

Description: The complexes [Ni 2 (L) 2 ] 2 · H 2 O ( 1 ) and [Cu 2 (L) 2 (H 2 O)] · 2CH 3 OH ( 2 ) were prepared by reaction of the chiral Schiff base ligand N -[(1 R ,2 S )-2-hydroxy-1, 2-diphenyl]-acetylacetonimine (H 2 L) with Ni II and Cu II ions, respectively, aiming to develop economically and environmentally-friendly catalysts for the hydrogenation of ketones. They have a dinuclear skeleton with axial vacant sites. The catalytic effects of the two complexes for hydrogenation of ketones were tested using dihydrogen gas as hydrogen source. They present some catalytic effects in hydrogenation of acetophenone, which has a dependence on the temperature and base used in these reactions. However, no apparent catalytic effects were found for the two complexes in hydrogenation of 4-nitroacetophenone and 4-methylacetophenone. Although the catalytic conversion in these hydrogenation reactions is low, they do represent a kind of cheap and environmentally-friendly hydrogenation catalyst.

Description: Poised to investigate the association of vanadium with physiological substrates in materials capable of exerting anticancer biological activity, pH-specific synthetic chemical reactivity between vanadium and triethyl ammonium acetate/trigonelline in aqueous and mixed organic-aqueous media led to the isolation of three new binary composite materials, namely K 2 [(MeN(+)C 5 H 4 COOH) 2 ][V 10 O 28 H 2 ] · 2H 2 O ( 1 ), [(H 2 N(+)Me 2 ) 4 ][V 10 O 28 H 2 ][Me 3 N(+)CH 2 COO(–)] 2 ( 2 ), and [(Me 3 N(+)CH 2 COOH) 4 ][V 10 O 28 H 2 ][Me 3 N(+)CH 2 COO(–)] 2 · 2H 2 O ( 3 ). 1–3 were characterized by elemental analysis, FT-IR and UV/Vis spectroscopy, Cyclic voltammetry, TGA-DTG, and X-ray crystallography. In all three compounds, the [V 10 O 28 H 2 ] 4– core unit is a common cluster assembly, with the vanadium in the +5 oxidation state. The counteracting cationic assembly in each composite material originates in the betaine starting reagent or the solvent out of which the materials crystallized. Biological activity studies of 1 and 3 in vitro in MCF-7 breast epithelial and A549 lung adenocarcinoma cell cultures show that both materials inhibit the viability of both cell lines in a dose-dependent fashion, in juxtaposition to the behavior of the betaine components present in these materials. Collectively, the herein studies a) reveal the uniquely defined synthetic methodologies and physicochemical properties of the variably assembled [V 10 O 28 H 2 ] 4– core units crystallized into the composite binary polyoxovanadate-betaine lattice structures, b) unravel the distinct cytotoxicity profile of the composite materials toward MCF-7 and A549 cells, and c) attest to their future potential as metallodrugs of pharmacological significance in anticancer activity.

Description: Long continuous seismic data recorded at five broadband seismic stations during 2006 at Campi Flegrei caldera have been analyzed. Introducing a coarse-grained method, we evaluate the time evolution of amplitude and polarization of the seismic noise in the frequency band common to Long-Period events. The series are modulated on tidal time scales: the root-mean square is basically dominated by solar contribution, while the azimuth of the polarization vector shows lunar diurnal and semidiurnal constituents. In addition, we find that in the frequency band common to Long-Period events the azimuths are polarized towards a specific area, suggesting that these persistent oscillations can be induced by the activity of the shallow geothermal reservoir.

Description: We report on the mineralogical assemblages found in the hyper-alkaline springs hosted on Liguria and Oman ophiolites based on exhaustive XRD and SEM analyses. In Liguria, hyper-alkaline springs produce a thin brownish calcite precipitate that covers the bedrock due to the concomitant atmospheric CO 2 uptake and neutralization of the hyper-alkaline waters. No brucite and portlandite minerals are observed. The discharge of alkaline waters in Oman ophiolite forms white-orange precipitates. Calcium carbonate minerals (calcite and/or aragonite) are the most abundant and ubiquitous precipitates and are produced by the same mechanism as in Liguria. This process is observed as a thin surface crust made of rhombohedral calcite. Morphological features of aragonite vary from needle-, bouquet-, dumbbell-, spheroidal-like habitus according to the origin of carbon, the temperature and the ionic composition of the hyper-alkaline springs, and the biochemical and organic compounds. Brucite is observed both at hyper-alkaline springs located at the thrust plane and at the paleo-Moho. The varying mixing proportions between the surface run-off waters and the hyper-alkaline ones control brucite precipitation. The Layered Double Hydroxide minerals occur solely in vicinity of hyper-alkaline springs emerging within the bedded gabbros. Finally, the dominant mineralogical associations we found in Oman (Ca-bearing carbonates and brucite) in a serpentinizing environment driven by the meteoric waters are surprisingly the same as those observed at the Lost City hydrothermal site in a totally marine environment.

Description: The crystal structures of the alkali aluminium thiohypodiphosphates M I AlP 2 S 6 (M I = Li, Na) are reported. NaAlP 2 S 6 crystallizes in the orthorhombic space group Fdd 2 (no. 43) with a = 8.0400(2), b = 10.9452(2), c = 20.8801(4) Å, and V = 1837.44(7) Å 3 ( Z = 8). It is isostructural with AgAlP 2 S 6 , which is consistent with the similar ionic radii of Na and Ag. In contrast, LiAlP 2 S 6 crystallizes in a different structure type which has not been observed in the large number of thiohypodiphosphates reported so far. It crystallizes in the monoclinic space group C 2/ c (no. 15) with a = 6.783(3), b = 10.365(4), c = 11.776(4) Å, β = 94.399(5)°, and V = 825.46(5) Å 3 ( Z = 4).

Description: We present the synthesis of 7-(diphenylphosphine)-indole 1 ( HPinol ) as a novel mono- and bidentate P - and N, P -ligand and its coordination chemical behaviour towards the d 6 - and d 8 -transition metals rhodium(III), palladium(II) and rhenium(I). The reaction of 1 with [Cp*RhCl 2 ] 2 in a 1:2 molar ratio leads to the formation of the P -coordinated complex [RhCl 2 ( P –( HPinol ))] ( 2 ). In the presence of the weak base NEt 3 , HCl elimination occurs by forming the neutral amido-phosphine chelated complex [RhCl( N, P –( Pinol ))] ( 3 ). The same P - and N, P -coordination is observed for palladium(II), where two ligands 1 coordinate to the metal centre forming the neutral complexes [PdCl 2 ( P – HPinol ) 2 ] ( 4 ) and [Pd( N, P – Pinol ) 2 ] ( 5 ). The reaction of Re(CO) 5 Br in the presence of NEt 3 and PPh 3 delivers the amido-phosphine complex [Re(CO) 3 PPh 3 ( N, P – Pinol )] ( 6 ). All products were characterised by multinuclear NMR spectroscopy, MS and IR spectra as well as elemental analysis. Furthermore, crystal structures of ligand 1 and all complexes 2–6 are presented.

Description: A computer program (PBUQ) that uses Monte Carlo simulations to propagate uncertainty through regression equations and the equation for the paleosol carbonate CO 2 paleobarometer is presented. PBUQ includes options for all of the common approaches to determining values for input variables and incorporates several recent advancements relevant to determining values for soil-respired CO 2 concentrations, δ 13 C values of respired CO 2 , δ 13 C values of atmospheric CO 2 and temperatures of soil carbonate formation. PBUQ is intended to improve confidence in paleoatmospheric CO 2 research by helping researchers draw statistically significant conclusions. PBUQ can also be used to attribute and partition error among various sources and thereby advance this technique. Sensitivity analysis indicates that S(z) is the largest source of uncertainty for most paleosols and that uncertainty is minimized for soils in which CO 2 is an evenly balanced mixture between soil-derived and atmospheric components. Evenly balanced mixtures are most likely for paleosols formed in deserts and for weakly-developed paleosols. Development of proxies for soil-respired CO 2 concentrations and δ 13 C values of soil-respired CO 2 specifically for such soils is perhaps the most crucial next step for improving this technique. Currently, calcic paleosols are best used to test the significance of trends and/or differences among time slices in paleoatmospheric CO 2 concentration. Application to quantifying Earth System Sensitivity will require large scale averaging of determinations from individual paleosols and/or reduced uncertainty associated with input variables.

Description: Long-lived detachment faults are now known to be important in tectonic evolution of slow-spreading mid-ocean ridges, and there is increasing evidence that fluid flow plays a critical role in development of detachment systems. Here we document a new manifestation of low-temperature hydrothermal venting associated with the detachment fault that formed Kane Megamullion ~3.3-2.1 m.y. ago in the western rift-valley wall of the Mid-Atlantic Ridge. Hydrothermal effects on the detachment surface include 1) cemented mounds of igneous rock and chalk debris containing hydrothermal Mn oxides and Fe oxyhydroxides, and 2) layered deposits of similar Fe-Mn minerals ± interbedded chalks. Mounds are roughly conical, ~1-10 meters high, and contain primarily basalts with lesser gabbro, serpentinite, and polymict breccia. The layered Fe-Mn-rich sediments are flat-bedded to contorted and locally are buckled into low-relief linear or polygonal ridges. We propose that the mounds formed where hydrothermal fluids discharged through the detachment hanging wall near the active fault trace. Hydrothermal precipitates cemented hanging-wall debris and welded it to the footwall, and this debris persisted as mounds as the footwall was exhumed and surrounding unconsolidated material sloughed off the sloping detachment surface. Some of the layered Fe-Mn-rich deposits may have precipitated from fluids discharging from the hanging-wall vents, but they also precipitated from low-temperature fluids venting from the exposed footwall through overlying chalks. Observed natural disturbance and abnormally thin hydrogenous Fe-Mn crusts on some contorted, hydrothermal Fe-Mn-rich chalks on ~2.7 Ma crust suggest diffuse venting that is geologically recent. Results of this study imply that there are significant fluid pathways through all parts of detachment systems and that low-temperature venting through fractured detachment footwalls may continue for several million years off-axis.

Description: P and S relative arrival time residuals from teleseismic earthquakes recorded on over 60 temporary AfricaArray broadband seismic stations deployed in Uganda, Tanzania and Zambia between 2007 and 2011 have been inverted, together with relative arrival time residuals from earthquakes recorded by previous deployments, for a tomographic image of mantle wave speed variations extending to a depth of 1200 km beneath eastern Africa. The image shows a low wave speed anomaly (LWA) well developed at shallow depths (100-200 km) beneath the Eastern and Western branches of the Cenozoic East African rift system and northwestern Zambia, and a fast wave speed anomaly at depths ≤ 350 km beneath the central and northern parts of the East African Plateau and the eastern and central parts of Zambia. At depths ≥350 km the LWA is most prominent under the central and southern parts of the East African Plateau and dips to the southwest beneath northern Zambia, extending to a depth of at least 900 km. The amplitude of the LWA is consistent with a ~150-300 K thermal perturbation, and its depth extent indicates that the African superplume, originally identified as a lower mantle anomaly, is likely a whole mantle structure. A superplume extending from the core-mantle boundary to the surface implies an origin for the Cenozoic extension, volcanism and plateau uplift in eastern Africa rooted in the dynamics of the lower mantle.

Description: In the Garibaldi Belt, the northern segment of the Cascade arc, basalts at Bridge River Cones, Salal Glacier, and Mt. Meager (BSM volcanic centers) are alkalic, atypical for an arc setting. Subduction signatures are negligible or absent from primitive alkalic basalts from Salal Glacier and Bridge River, while altered oceanic crust may have contributed a minimal amount of fluid at Mt. Meager. More evolved BSM basalts display trace element signatures considered typical of arc lavas, but this is a consequence of deep crustal assimilation rather than primary input from the subducted slab. Primary BSM basalts represent 3-8% melts that segregated from enriched garnet lherzolite at significantly higher temperatures and pressures (70-105 km) than calc-alkaline Cascade arc basalts. The BSM mantle source is significantly more incompatible element-enriched than the depleted mantle tapped by calc-alkaline Cascade arc basalts. The BSM basalts are also isotopically distinct from calc-alkaline Cascade arc basalts, more similar to MORB and intraplate basalts of the NE Pacific and NW North America. The relatively deep, hot, and geochemically distinct mantle source for BSM basalts is consistent with upwelling asthenosphere. The BSM volcanic centers are close to the projected trace of the Nootka fault, which forms the boundary between the subducting Juan de Fuca plate and the near-stagnant Explorer plate. A gap or attenuated zone between the plates may promote upwelling of enriched asthenosphere that undergoes low-degree decompression melting to generate alkalic basalts that are essentially free of slab input yet occur in an arc setting.

Description: The temporal evolution of the mantle melting processes in the Asal Rift is evaluated from the chemical composition of 56 new lava flows sampled along 10 km of the rift axis and 9 km off-axis (i.e., erupted within the last 620 ky). Petrological and primary geochemical results show that most of the samples of the inner floor of the Asal Rift are affected by plagioclase accumulation. Trace element ratios and major element compositions corrected for mineral accumulation and crystallization show a symmetric pattern relative to the rift axis and preserved a clear signal of mantle melting depth variations. While FeO, Fe 8.0 , Zr/Y and (Dy/Yb) N decrease from the rift shoulders to the rift axis, SiO 2 , Na/Ti, Lu/Hf increase and Na 2 O and Na 8.0 are constant across the rift. These variations are qualitatively consistent with shallow melting beneath the rift axis and deeper melting for off-axis lava flows. Na 8.0 and Fe 8.0 contents show that beneath the rift axis, melting paths are shallow, from 81 ± 4 km to 43 ± 5 km. These melting paths are consistent with adiabatic melting in normal-temperature fertile asthenosphere, beneath an extensively thinned mantle lithosphere. On the contrary, melting on the rift shoulders (from 107 ± 7 km to 67 ± 8 km) occurred beneath thicker lithosphere, requiring a mantle solidus temperature 100 ± 40 °C hotter. In this geodynamic environment, the calculated rate of lithospheric thinning appears to be 4.0 ± 2.0 cm yr -1 , a value close to the mean spreading rate (2.9 ± 0.2 cm yr -1 ) over the last 620 ky.

Description: Global Positioning System (GPS) and Differential Interferometric Synthetic Aperture Radar (DInSAR) data, collected from July 2007 to July 2008 on Mt. Etna, are analysed to define the dynamics preceding and accompanying the onset of the eruption on 13 May 2008. Short and long-term comparisons have been made on both GPS and radar data, covering similar time windows. Thanks to the availability of three GPS surveys the year before the eruption onset, an increase in the seawards movement of the NE flank of the volcano has been detected in the few months before the dike intrusion. The GPS ground deformation pattern also shows a slight inflation centred on the western side of the volcano in the pre-eruptive long-term comparison (from July 2007 to May 2008). The GPS has been integrated with DInSAR data by the SISTEM approach, to take advantage of the different methodologies and provide high spatial sampling of the 3D ground displacement pattern. We inverted the SISTEM results in order to model the pressure source causing the observed pre-eruptive inflation. The subsequent emplacement of the eruptive dike was imaged by two GPS surveys carried out on a dense network over the uppermost part of the volcano on May 6 and 13, i.e. a few days before and a few hours after the beginning of the eruption. We inverted this comparison to define the position, geometry and kinematics of the dike. The dike intrusion was also imaged by DInSAR data with temporal baselines of 2-3 months, which confirm strong displacements localized on the summit area, rapidly decreasing towards the middle flanks of the volcano, as detected by very short-term GPS data; furthermore, the comparison between DInSAR and GPS data highlighted the presence of a depressurizing source localized beneath the upper south-western area, acting just after the dike intrusion. Finally, the long period (one year) GPS and DInSAR data were integrated by SISTEM in order to finely depict the 3D ground deformation pattern with the highest spatial resolution. The long-period data allowed the complex kinematics of the volcano to be finely imaged and highlighting the interaction between flank dynamics and magma injection.

Description: In the course of investigations relating to magnesia oxysulfate cement the basic magnesium salt hydrate 3Mg(OH) 2 · MgSO 4 · 8H 2 O (3–1–8 phase) was found as a metastable phase in the system Mg(OH) 2 -MgSO 4 -H 2 O at room temperature (the 5–1–2 phase is the stable phase) and was characterized by thermal analysis, Raman spectroscopy, and X-ray powder diffraction. The complex crystal structure of the 3–1–8 phase was determined from high resolution laboratory X-ray powder diffraction data [space group C 2/ c , Z = 4, a = 7.8956(1) Å, b = 9.8302(2) Å, c = 20.1769(2) Å, β = 96.2147(16)°, and V = 1556.84(4) Å 3 ]. In the crystal structure of the 3–1–8 phase, parallel double chains of edge-linked distorted Mg(OH 2 ) 2 (OH) 4 octahedra run along [–110] and [110] direction forming a pattern of crossed rods. Isolated SO 4 tetrahedra and interstitial water molecules separate the stacks of parallel double chains.

Description: The cover picture shows the synthesis and the molecular structure of a zwitterionic [4.3.0]-bicyclic aluminum-phosphorus compound with annulated C 3 P 2 and Al 2 C 2 PH heterocycles and a 3c-2e Al–H–Al bond. Treatment of the dialkynylphosphine Mes–P(–C=C–CMe 3 ) 2 ( 1 ) with diethylaluminum hydride ( 2 ) in an equimolar ratio afforded a mixture of compounds, in which a [3.2.0]-bicyclic compound 3 with annulated fourmembered AlC 2 P and five-membered P 2 C 3 heterocycles could be identified by NMR spectroscopy. Excess of the hydride 2 yielded small quantities of the zwitterionic [4.3.0]-bicyclic compound 4 , which formally resulted from the unique insertion of a diethylaluminum hydride molecule into the Al–C(vinyl) bond of the strained fourmembered heterocycle of 3 . A six-membered ring is formed which contains an Al–H–Al 3c-2e bond. More details can be found in the Article by Werner Uhl et al. on page 1181 ff.

Description: A regional survey of alkaline springs in Oman and Ligurian ophiolites shows that the alkaline water compositions significantly vary from one ophiolite to the other and within the same ophiolite. The first order correlation between the Na (and K) and Cl concentrations points to fluid compositions only partly due to evaporation. The scatter around the evaporation line implies that Na and Cl may not be conservative during the alteration of the ultramafic rocks. Mg is almost entirely depleted at pH 〉 10.5 as a result of serpentine formation within the ultramafic body and of brucite (and minor hydrotalcite) precipitation at the springs. Ca accumulates in the high pH fluids and is consumed by Ca-carbonate formation at the springs, by mixing with river waters or by the CO2 supply from the atmosphere. Thermodynamic calculations show that brucite saturation is reached at pH values around 10.5 which triggers major changes in the water composition. The waters evolve from a quartz-saturated low pH continental environment to a brucite-dominated high pH serpentinizing system at low temperature. The highest water salinities are found in springs located along the basal thrust plane of the ophiolite. The highest Al concentrations are found in some springs located on the crustal side of the mantle/crust boundary. This poses the question of the hydrologic pathways and of the role of the mineralogical composition of the altered formations.

Description: Using the bis(pyrazolyl)pyridinylmethane ligand α,α,α-bis(1-pyrazolyl)(2-pyridinyl)toluene {(ph)C(pz) 2 (py)} for bioinorganic inspired coordination chemistry studies, we synthesised and structurally characterised three monofacial complexes [{(ph)C(pz) 2 (py)}CoCl 2 ] ( C1 ), [{(ph)C(pz) 2 (py)}CuCl 2 ] ( C2 ), [{(ph)C(pz) 2 (py)}ZnCl 2 ] ( C3 ) and the binuclear halogenido-bridged complexes [{(ph)C(pz) 2 (py)} 2 (μ-Cl) 2 Fe 2 Cl 2 ] ( C4 ) and [{(ph)C(pz) 2 (py)} 2 (μ-Br) 2 Cu 2 Br 2 ] ( C5 ). In four of these complexes, severe disorders between pyrazolyl and pyridinyl donor groups are observed such that bis(pyrazolyl) and (pyrazolyl)(pyridinyl) coordination modes are concomitantly found. The donor competition is dissected by DFT calculation of the energy differences between the two coordination modes and NBO analysis of the donor situation. The pyrazolyl units provide with more donor strength although pyridine is considerably more basic.

Description: Metal ions poisoning can result from environmental factors, intentional action, or disruption of homeostasis. Although the origin of toxicity may be different, the treatment is similar. Chelation therapy aims to remove the excess of metal ions from tissues to stop further damage of cells. For almost every metal ion, molecules that are able to bind it and remove from the human body are known. Over the years some new chelating agents were discovered and introduced into clinical treatment. In this paper we have focused on typical chelators for metal ions, both essential and toxic for humans. The treatment of poisoning caused by essential metal ions is hard due to the risk of removing them from the biologically relevant molecules (e.g. enzymes). Acute metal ions poisoning is rather rare, so the development of chelators for such cases are historical, but prolonged toxicity of, especially, essential metal ions is extensively studied.

Description: The reactions of [Os(NO)Cl 5 ] 2– with glycine (GlyH), picolinic acid (PicoH), L -proline ( L -ProH) and D -proline ( D -ProH) afforded four novel complexes of the general formula [Os(NO)Cl 3 (AA)] – , where AA = Gly, Pico, L -Pro and D -Pro, respectively. X-ray diffraction studies have revealed that in all cases the same isomer type from three theoretically possible, has been isolated, namely mer (Cl), trans (NO, O)-[Os(NO)Cl 3 (AA)] – . Spectroscopic and electrochemical properties, behavior in aqueous solution and antiproliferative activity in three human cancer cell lines are also reported.

Description: The electron distributions in position and in momentum space of the hcp metals magnesium and zinc are investigated experimentally and compared to results of quantum-chemical calculations. Furthermore, a survey is given on recent analyses of the bonding properties of zinc and cadmium, using the method of increments. The experimental deformation densities were obtained by refining multipole models to X-ray diffraction data sets measured at 100 K with either Mo- K α (Mg) or Ag- K α (Zn) radiation. The final R F values (Valray/Jana2006) are 0.0028/0.0034 (Mg) and 0.0068/0.0068 (Zn). The differences to deformation densities obtained from periodic density functional calculations are discussed. The effect of dynamical electron correlation on the electron density was analyzed, using cluster models. Compton profiles were measured with 88.67 keV synchrotron radiation at beamline ID15B at the ESRF in Grenoble. Varied orientations of the samples allowed for probing the projected momentum distribution along the [100], [423] and [001] directions. Fourier transforms of the computed reciprocal form factor B ( r ) resulted in the corresponding theoretical Compton profiles. It is suggested that the anomalous hcp structure of zinc is favored by a kinetic balancing of the valence electrons, i.e. correlation mediated 4 s -3 d interactions.

Description: . This Research Report provides an overview on synthesis, structure, and reactivity of the recently discovered carboranylamidinate ligands. Carboranylamidinate anions of the type [( o -C 2 B 10 H 10 C(NHR)(=N R )] – ( R = i Pr, cyclohexyl) are readily accessible via addition of o -lithiocarborane to N , N ′-carbodiimides R –N=C=N– R . They combine the highly versatile characteristics of both amidinates and carboranes in one unique ligand system. Unlike simple amidinate anions, the carboranylamidinates coordinate to metal ions not as typical N , N ′-chelating ligands but adopt an unexpected κ 2 C, N -bonding mode. The free imine functionality in carboranylamidinates can be further deprotonated. The resulting dianions were demonstrated to be excellent starting materials for novel boron-rich heterocycles incorporating e.g. Si, Sn, P, or transition metals such as Ti, Zr, Rh, and Ir. Further modification of the carboranylamidinate cage structure includes the introduction of additional functional groups like –SH or –SeH as well as the selective removal of a boron atom with formation of novel nido -type dicarbollylamidinate ligands. An initial study already showed that transition metal carboranylamidinates are potentially useful as polymerization catalysts.

Description: KSbWO 6 was prepared by sol-gel method. N-doped KSbWO 6 (KSbWO 6– x N x ) was obtained by heating KSbWO 6 and urea at 400 °C. Both the compounds are characterized by powder X-ray diffraction (XRD), TEM, SEM-EDS, X-ray photo electronic spectroscopy (XPS), and UV/Vis diffuse reflectance spectroscopy (UV-DRS). A shift in the peak positions of powder XRD and XPS spectra was observed. The band gap energy ( E g ) of KSbWO 6 and N-doped KSbWO 6 was obtained from their diffused reflectance spectra. E g was reduced from 3.17 eV to 2.56 eV upon nitrogen doping in KSbWO 6 . The reduction of the E g is attributed to the lifting of valence band of N-doped KSbWO 6 , due to the mixing of O 2p states with N 2p states. The photocatalytic activity of both the samples was studied by degradation of methylene blue (MB). The nitrogen doped KSbWO 6 shows higher photocatalytic activity compared to that of KSbWO 6 .

Description: [1]  This study examines the effect of gas hydrate formation on seismic wave velocities of fine-grained sediments. Synthesis of gas hydrates in fine-grained sediments has proved to be challenging, and how hydrate formation would affect the seismic wave velocities and stiffness of clay-rich sediments has not yet been fully understood. In this study, CO 2 hydrate was synthesized in remolded and partially water-saturated clayey silt sediments that were originally cored from a hydrate occurrence region in the Ulleung Basin, East Sea, offshore Korea. After achieving excess water conditions, compressional wave and shear wave velocities were measured for different hydrate saturations and under different vertical effective stresses. The results reveal that the compressional wave velocity V P and shear wave velocity V S increase and the stress-dependency of V P and V S decreases as the hydrate saturation S H increases from 0% to ~60%. In particular, the V S ‒S H trend lies between the grain-cementing model and the load-bearing model, suggesting that gas hydrate formation in clayey silt sediments causes weak cementation from a hydrate saturation less than ~28%. The weak cementation in fine-grained sediments can be explained by the breakage of hydrate bonds that are cementing grains during sediment compression and/or the innate weakness in bonding between hydrate crystals and fine mineral grains owing to the presence of unfrozen water films on clay mineral surfaces. In addition, it is found that at low S H the cementation effect on V P is masked by the high stiffness of pore-filling phases, but it becomes pronounced at S H greater than 47%.

Description: [1]  Mountain rivers play a key role in the delivery of particulate organic carbon (POC) to large river systems and the ocean. Due to the extent of its drainage area and runoff, the Amazon River is one of Earth's most important biogeochemical systems. However the source of POC eroded from the humid region of the Eastern Andes and the input of fossil POC from sedimentary rocks (POC fossil ) remains poorly constrained. Here we collected suspended sediments from the Kosñipata River during flood events to better characterise Andean POC, measuring the nitrogen to organic carbon ratio (N/C), stable carbon isotopes ( δ 13 C org ) and radiocarbon ( Δ 14 C org ). Δ 14 C org values ranged from -711‰ to -15‰ and significant linear trends between Δ 14 C org, N/C and δ 13 C org suggested that this reflects the mixing of POC fossil with very young organic matter ( Δ 14 C org  ~ 50‰) from the terrestrial biosphere (POC non-fossil ). Using N/C and Δ 14 C org in an end member mixing analysis, we quantify the fraction of POC fossil (to within 0.1) and find that it contributes a constant proportion of the suspended sediment mass (0.37 ± 0.03%) and up to 80% of total POC. In contrast, the relative contribution of POC non-fossil was variable, being most important during the rising limb and peak discharges of flood-events. The new data shed light on published measurements of ‘old’ POC (low Δ 14 C org ) in Andean-fed tributaries of the Amazon River, with their Δ 14 C org and δ 13 C org values consistent with variable addition of POC fossil . The findings suggest a greater persistence of Andean POC in the lowland Amazon than previously recognised.

Description: [1]  The D’ Entrecasteaux Island (DEI) gneiss domes are fault-bounded domes with ~2.5 km of relief exposing ultrahigh-pressure (UHP) and high-pressure (HP) metamorphic gneisses and migmatites exhumed in an Oligocene-Miocene arc-continent collision and subduction zone subject to Late Miocene to Recent continental extension. Multi-channel seismic (MCS) reflection data and well data show the Trobriand basin formed as a forearc basin caused by southward Miocene subduction at the Trobriand trench. Subduction slowed at ~8 Ma as the margin transitioned to an extensional tectonic environment. Since then, the Trobriand basin has subsided 1–2.5 km as a broad sag basin with few normal faults deforming the basin fill. South of the DEI, the Good enough rift basin developed after extension began (~8 Ma) as the hanging-wall of the north-dipping Owen-Stanley normal fault that bounds the basin's southern margin. The lack of upper crustal extension accompanying subsidence in the Trobriand and Good enough basins suggests depth-dependent lithospheric extension since 8 Ma has accompanied uplift of the DEI gneiss domes. Structural reconstructions of seismic profiles show 2.3 to 13.4 km of basin extension in the upper crust, while syn-rift basin subsidence values indicate at least 20.7 to 23.6 km of extension occurred in the entire crust since ~8 Ma. Results indicating thinning is preferentially accommodated in the lower crust surrounding the DEI are used to constrain a schematic model of uplift of the DEI domes involving vertical exhumation of buoyant, post-orogenic lower crust, far-field extension from slab rollback, and an inverted two-layer crustal density structure.

Description: [1]  The relationship between lithospheric evolution of eastern Eurasia and subduction of the Pacific plate has long been debated. However, the timing and implications of subduction on the tectonics of eastern China are not well constrained. Here, we present new zircon U-Pb ages and Hf isotopes, elemental and Sr-Nd-Pb isotopic data on Cretaceous volcanic rocks from the Ningwu basin, eastern China to further address this issue. Our age data reveal rapid eruption of the volcanic rocks within a short duration from 133 to 130 Ma. The rocks, mostly characterized by shoshonitic and high-K calc-alkaline signatures, display light rare earth element and Pb enrichment, Nb, Ta and Ti depletion, highly radiogenic Sr-Pb isotopic ratios and variable ε Hf (t) (+1.8 to −10), suggesting derivation from an enriched lithospheric mantle metasomatized by marine sediments. The early lavas (133.3 ± 1.1 Ma) show stronger subducted-related signatures than the late lavas (130.1 ± 1.0 Ma), which we interpret to reflect consumption of a significant volume of fusible subducted components in the early melting phase. The large ε Hf (t) variation of late lavas suggests greater involvement of asthenospheric melts and lower crust in their petrogenesis. The youngest age (130 Ma) appears to coincide with an inferred change in the direction of Pacific-Eurasia convergence, manifested as a change from extension to transpression in eastern China. The narrow window of eruption may signify a rapid change of the tectonic regime in the Early Cretaceous.

Description: Mid-ocean ridges magmatism is by and large considered to be mostly dry. Nevertheless, numerous works in the last decade have shown that a hydrous component is likely to be involved in ocean ridges magmas genesis and / or evolution. The petrology and geochemistry of peculiar coarse grained gabbros sampled in the upper part of the gabbroic sequence from the Northern Oman ophiolite (Wadi Rajmi) provide information on the origin and fate of hydrous melts in fast spreading oceanic settings. Uncommon crystallization sequences for oceanic settings (clinopyroxene crystallizing before plagioclase), extreme mineral compositions (plagioclase An% up to 99, and clinopyroxene Mg# up to 96), and the presence of magmatic amphibole, imply the presence of a high water activity during crystallization. Various petrological and geochemical constraints point to hydration resulting from the recycling of hydrothermal fluids. This recycling event may have occurred at the top of the axial magma chamber where assimilation of anatectic hydrous melts is recurrent along mid-ocean ridges, or close to segments ends where fresh magma intrudes previously hydrothermally altered crust. In ophiolitic settings, hydration and remelting of hydrothermally altered rocks producing hydrous melts may also occur during the obduction process. Although dry magmatism dominates oceanic magmatism, the dynamic behavior of fast spreading ocean ridge magma chambers has the potential to produce the observed hydrous melts (either in ophiolites or at spreading centers), which are thus part of the general mid-ocean ridges lineage.

Description: The Seismic Array HiKurangi Experiment (SAHKE) investigated the structure of the forearc and subduction plate boundary beneath the southern North Island along a 350 km transect. Tomographic inversion of first-arrival travel times was used to derive a 15-20 km deep P-wave image of the crust. The refracted phases and migrated reflection events image subducting slab geometry and crustal structure. In the west, Australian Plate Moho depth decreases westward across the Taranaki Fault system from 35 to ~28-30 km. In the east, subducted Pacific Plate oceanic crust is recognised to have a positive velocity gradient, but becomes less distinct beneath the Tararua Ranges, where the interface increases in dip at about 15 km depth from 〈5° to 〉15°. This bend in the subducted plate is associated with vertical clusters in seismicity, splay fault branching, and low-velocity high-attenuation material that we interpret to be an underplated subduction sedimentary channel. We infer that a step down in the decollément transfers slip on the plate interface at the top of a subduction channel to the oceanic crust and drives local uplift of the Tararua Ranges. Reflections from the Wairarapa Fault show that it is listric and soles into the top of underplated sediments, which in turn abut the Moho of the over-riding plate at ~32 km depth, near the downdip end of the strongly locked zone. The change in dip of the Hikurangi subduction interface is spatially correlated with the transition from geodetically determined locked to unlocked areas of the plate interface.

Description: The chemistry of cytotoxic platinum(II) complexes is more or less restricted to ligand exchange reactions, derivatization of coordinated ligands is cumbersome, and subsequent purification in many cases impossible. Consequently, kinetically more inert platinum(IV) complexes found their way into the development of novel, promising anticancer drugs. Research has focused more and more during the last years on the use of platinum(IV) complexes featuring one or two axial succinato ligands in which one carboxylic acid moiety is available for further derivatization. In order to gain a deeper insight into the mechanism of action, isotopically labeled platinum(IV) complexes with axial (1,4– 13 C 2 )succinato ligands were synthesized and fully characterized by multinuclear ( 1 H, 13 C, 15 N, and 195 Pt) 1D- and 2D-NMR spectroscopy. Especially of note in this context is a long range 1 H, 13 C shift correlation signal detected between the equatorial ammine protons and the axially coordinated carboxylato moiety. Furthermore, their behavior in extracts of SW480 cancer cells was investigated. Preliminary results demonstrate that cisplatin analogs are reduced significantly faster in comparison to carboplatin analogs.

Description: The Cu II solution chemistry of synthetic derivatives of naturally occurring pseudo-octapeptides (patellamides and ascidiacyclamide) is described. The complex stabilities [mono- and dicopper(II) complexes] of five different ligands were determined by isothermal microcalorimetry (ITC), and square wave voltammetry (SQW) was used to elucidate the electrochemical properties. In agreement with published spectroscopic data, there is cooperative binding of two Cu II ions and the overall stabilities are, in agreement with known stabilities of the natural ligands and expectations based on the donor sets (two N-based heterocycles and one amide per Cu II ), only moderate ( K ≤ 10 6 ). There is a slight dependence of the stabilities on the ligand structure (configuration of the side chains), and that derived from the natural products forms the most stable complexes. Due to the complex equilibria in solution and the instability of the reduced forms, voltammetry shows complex equilibria, which preclude the full assignment of all processes. The positive reduction potentials are in agreement with relatively low complex stabilities. These observations complete earlier studies, concentrating on spectroscopy and structural aspects, and are also discussed in relation to the possible biological function of the cyclic peptides, i.e. metal ion transport, oxygen activation, carboanhydrase, and phosphatase activities.

Description: Setting out from protected L -cysteine a 2,5-diketopiperazine V can be synthesized, the reduction of which with NaBH 4 /TiCl 4 leads to (6 R ,8 aR )-7-methyl-6-(sulfanylmethyl)-thiazolidine [3,4- a ] piperazine, L 1 H as well as N , N ′-dimethyl-(2 R ,5 R )-bis(sulfanylmethyl) piperazine, L 2 H 2 , which were separated and characterized. L 2 H 2 can be obtained selectively, if V is reduced by NaBH 4 /TiCl 4 in the presence of DIEA · HCl, and it represents a precursor for a novel, chiral ligand, as after deprotonation it provides two thiolato and two amino donor functions for the coordination of a metal atom. Deprotonation of L 1 H and L 2 H 2 with NaOMe followed by treatment with NiBr 2 (dme) led to the isolation of the dimeric complexes [L 1 NiBr] 2 ( 1 ) and [L 2 Ni] 2 ( 2 ), respectively. Both were fully characterized, and cyclic voltammetry indicated the possibility of Ni II → Ni III oxidations for complex 2 . 2 can be regarded as a structural model for the A clusters of the acetyl coenzyme A synthase.

Description: [1]  The origin of crustal-scale silicic magmatism remains a matter of debate, and notable uncertainty exists concerning the physical mechanisms that drive ascent and emplacement of felsic magmas in upper crustal regions. A 2D numerical model demonstrates that injection of mantle-derived mafic magma into a partially molten hot zone in the lower crust can drive felsic magma ascent and intrusion into upper crustal levels. The injection of mafic magma induces over pressure in the reservoir, which increases crustal stresses and triggers development of brittle/plastic shear zones, and can drive significant surface uplift. The emerging topography causes a non-uniform over pressure distribution in the reservoir and can trigger felsic magma ascent along crustal shear zones. Based on systematic numerical experiments we investigate the influence of crustal strength and injection rate. The initial upper crustal strength controls the degree of crustal faulting and surface uplift and, therefore, whether felsic magma ascent can be initiated or not. The final upper crustal strength influences the depth and final style of felsic intrusion. The injection rate of mafic magma determines the time scale of overpressure growth and surface uplift stage. In contrast, the duration of the subsequent felsic ascent and intrusion emplacement stages remains nearly constant. Our results imply that mafic underplating and intrusion into the lower crust may not only be a prime control for the generation of felsic magmas in the lower crust, but may also be an important physical driving mechanism for felsic magma ascent and intrusion into upper crustal levels.

Description: A new chiral racemic ligand ( o -carboranyl)bis(2-hydroxymethyl)pyridine oCB(hmpH) 2 , that is composed of a central o -carborane unit where two arms radiate out of the cluster carbons each one containing a 2-pyridylmethylalcohol chelating arms, provides two potentially bidentate {NO} or one tetradentate {N 2 O 2 } binding pockets. An unprecedented octahedral Co II complex [CoCl 2 ( anti - oCB (hmpH) 2 ] was obtained under aerobic conditions and characterized by X-ray crystallography as well as IR and NMR spectroscopy. anti - oCB (hmpH) 2 acts as a tetradentate N 2 O 2 -ligand affording the complex as a racemic mixture of cis- α Δ-[CoCl 2 ( RR anti - oCB (hmpH) 2 )] and Λ-[CoCl 2 ( SS anti - oCB (hmpH) 2 )]. The new ligand oCB(hmpH) 2 appears to be suitable for producing a variety of new chiral-at-metal complexes.

Description: Abstract. The title compounds NH 4 [Cu(S 2 CNH 2 ) 2 ] · H 2 O (A) and CuS 2 CNH 2 (B) were prepared from aqueous alcoholic solutions by reaction of ammoniumdithiocarbamate with copper sulfate in presence of excess cyanide as reductive. (A) crystallizes in the orthorhombic space group C 222 1 (No. 20) with a = 8.9518(6), b = 9.6414(6) and c = 10.6176(8) Å, Z = 4. (B) crystallizes in the orthorhombic space group P 2 1 2 1 2 1 (No. 19) with a = 5.9533(4), b = 6.6276(4) and c = 9.4834(5) Å, Z = 4. In the crystal structure of (A) copper has a tetrahedral surrounding of four monodentate dithiocarbamate ligands. These structural units form 2D nets stacked along [001]. Staggered chains consisting of H 2 O and NH 4 + penetrate the crystal structure along [001] yielding additional coherence via hydrogen bonds. The crystal structure of (B) comprises a three-dimensional tetrahedral framework of CuS 4 units exclusively linked by vertices. The arrangement is reminiscent of a filled β -cristobalite structure with the dithiocarbamate ligands extending into the hollow spaces. Thermal decomposition precedes stepwise finally giving Cu 2 S in each case.

Description: A thorough study on the thermoelectric potential of the layered compound SnBi 2 Te 4 is presented. Phase range studies on SnBi 2 Te 4 , unit cell parameters by powder X-ray diffraction, and electronic structure calculations (both LDA and GGA functional) were performed. Physical property measurements regarding substitution of tin and bismuth with the triel ( Tr = Ga, In, Tl) elements are presented towards the improvement of thermoelectric properties, according to Tr x Sn 1– x Bi 2 Te 4 and Tr x SnBi 2– x Te 4 . The range of inclusion was generally over 0.01 ≤ x ≤ 0.15 to monitor compound changes as well as phase purity limits. Seebeck coefficient, S , electrical conductivity, σ , and thermal conductivity, κ , were measured, yielding the dimensionless Figure of merit, ZT , data over a temperature range between 300 K and 680 K. Results of partial replacements of tin and bismuth are compared and reported. ZT max values range from 0.10 to 0.34 depending on the dopant, achieved at temperatures from 355 K to 420 K.

Description: A new two-step procedure for the synthesis of MoS 2 nanotubes using lead as a growth promoter is reported. In the first step, molybdenum suboxide nanowhiskers containing a small amount of lead atoms were created by exposing a pressed MoS 2 +Pb mixture to highly compressed shock-heated argon gas, with estimated temperatures exceeding 9900 K. In the second step, these molybdenum suboxide nanowhiskers served as templates for the sulfidization of the oxide into MoS 2 nanotubes (by using H 2 S gas in a reducing atmosphere at 820 °C). Unlike the case of WS 2 nanotubes, the synthesis of a pure phase of MoS 2 nanotubes from molybdenum oxide has proven challenging, due mostly to the volatile nature of the latter at the high requisite reaction temperatures (〉800 °C). In contrast, the nature and apparent reaction mechanism of the method reported herein are amenable to future scale-up. The high-temperature shockwave system should also facilitate the synthesis of new nanostructures from other layered materials.

Description: The reaction of RuCl 2 (PPh 3 ) 3 with N -pyrazolylpropanamide ( N -ppa) displaces a single PPh 3 producing the six-coordinate complex RuCl 2 (PPh 3 ) 2 ( N -ppa) ( 1 ). A crystal structure determination of the dichloromethane solvate RuCl 2 (PPh 3 ) 2 ( N -ppa) · 2CH 2 Cl 2 ( 1·2CH 2 Cl 2 ) revealed that the geometry about the central Ru atom is distorted octahedral with the chloride ligands in trans -position and the N -ppa acting as N , O -chelating ligand. In the solid state, RuCl 2 (PPh 3 ) 2 ( N -ppa) molecules are dimerized via N–H ··· Cl hydrogen bonds. The dimers pack as chains in the c direction and form voids that are occupied by dichloromethane solvent molecules.

Description: Four complexes with supramolecular architectures, namely, MZCA · 3H 2 O ( 1 ), [Zn(H 2 O) 6 ] 2+ · [MZCA] 2 · [H 2 O] 6 ( 2 ), [Mn(MZCA) 2 (H 2 O) 4 ] · 2H 2 O ( 3 ), and [Ni(MZCA) 2 (H 2 O) 4 ] · 2H 2 O ( 4 ) [MZCA = 3-(carboxymethyl)-2, 7-dimethyl-3H-benzo[d]imidazole-5-carboxylic acid], were synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complexes 1 and 2 display a remarkable 3D network with 1D hydrophilic channels. Complexes 3 and 4 are isostructural and exhibit a 3D structure encapsulating 1D 24-membered ring microporous channels. The UV/Vis and fluorescent spectra were measured to characterize complexes 1 – 4 . The thermal stability of complexes 2 – 4 were also examined.

Description: The transition metal dihydrogen hypodiphosphate hydrates K 2 [Co(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 1 ), K 2 [Ni(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 2 ), K 2 [Cu(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 3 ) and K 2 [Zn(H 2 P 2 O 6 ) 2 (H 2 O) 2 ] · H 2 O ( 4 ) were synthesized and characterized by single crystal structure determination. The compounds 1 – 4 crystallize isotypic in the monoclinic space group C 2/ m (no. 12) with two formula units in the unit cell. The crystal structure is built up by [H 2 P 2 O 6 ] 2– units in an eclipsed conformation, by the corresponding transition metal, potassium cations, and water molecules. The eclipsed conformation of the [H 2 P 2 O 6 ] 2– has not been previously observed in none of known hypodiphosphates(IV) analyzed via X-ray diffraction. However, its proposed based on spectroscopic methods. FT-IR/FIR and FT-Raman spectra of the crystalline salts were recorded and the thermal behavior of the compounds was investigated.

Description: Two coordination polymers, [Co 2 (Hcpip) 2 (phth)] n · 3 n (H 2 O) ( 1 ) and [Mn 2 (Hcpip) 2 (phth)] n ( 2 ), {H 2 cpip = 2-(2-carboxyphenyl)imidazo[4,5-f](1,10)- phenanthroline, H 2 phth = phthalic acid}, were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, and single-crystal X-ray diffraction. Complex 1 is a 1D chain, in which the dinuclear [Co 2 (Hcpip) 2 ] 2+ units are linked through (phth) 2– anions. Complex 2 is a 2D layer structure, which is constructed from the 1D chains bridged by (phth) 2– anions. The magnetic properties of 1 and 2 show that the weak ferromagnetic interactions occurred between Co II ions in 1 and a weak antiferromagnetic interactions exist between Mn II ions in 2 . These two complexes have good thermal stabilities.

Description: The Paleocene-Eocene Thermal Maximum (PETM) is marked by a prominent negative carbon isotope excursion (CIE) of 3-5‰ that has a characteristic rapid onset, stable body, and recovery to near pre-CIE isotopic composition. Although the CIE is the major criterion for global correlation of the Paleocene-Eocene boundary, spatial variations in the position and shape of the CIE have not been systematically evaluated. We measured carbon isotope ratios of bulk organic matter (δ 13 C org ) and pedogenic carbonate (δ 13 C carb ) at six PETM sections across a 16 km transect in the SE Bighorn Basin, Wyoming. Bed tracing and high-resolution floral and faunal biostratigraphy allowed correlation of the sections independent of chemostratigraphy. The onset of the CIE in bulk organic matter at all six sections occurs within a single laterally extensive geosol. The magnitude of the CIE varies from 2.1-3.8‰. The absolute and relative stratigraphic thickness of the body of the CIE in bulk organic matter varies significantly across the field area and under-represents the thickness of the PETM body by 30%-80%. The variations cannot be explained by basinal position and instead suggest that δ 13 C org values were influenced by local factors such as reworking of older carbon. The stratigraphic thickness and shape of the CIE have been used to correlate sections, estimate timing of biotic and climatic changes relative to the presumed carbon isotope composition of the atmosphere, and calculate rates of environmental and biotic change. Localized controls on δ 13 C org values place these inferences in question by influencing the apparent shape and duration of the CIE.

Description: Three tungsten oxychloride clusters containing the nearly D 3 d symmetric [(W 6 O 6 i Cl 6 i )Cl 6 a ] n – ( n = 2, 3) core were prepared from the cluster acid (H 5 O 2 ) 2 [W 6 O 6 Cl 12 ] · 4H 2 O and structurally characterized by single-crystal X-ray diffraction. The copper compound [Cu(H 2 O) 4 ][W 6 O 6 Cl 12 ] · 12H 2 O releases water molecules to yield [Cu(H 2 O) 6 ][W 6 O 6 Cl 12 ]. Both compounds are represented as diamagnetic clusters, having 14 electrons in W–W bonding states. Magnetic measurements on the calcium compound [Ca(H 2 O) 7 ] 2 [W 6 O 6 Cl 12 ]Cl revealed a paramagnetic cluster having 15 valence electrons.

Description: Estimates of the relative motion between the Hawaiian and Louisville hotspots have consequences for understanding the role and character of deep Pacific-mantle return flow. The relative motion between these primary hotspots can be inferred by comparing the age records for their seamount trails. We report 40 Ar/ 39 Ar ages for 18 lavas from 10 seamounts along the Hawaiian-Emperor Seamount Chain (HESC), showing that volcanism started in the sharp portion of the Hawaiian-Emperor Bend (HEB) at ≥47.5 Ma and continued for ≥5 Myr. The slope of the along-track distance from the currently active Hawaiian hotspot plotted versus age is constant (57±2 km/Myr) between ~57 and 25 Ma in the central ~1900 km of the seamount chain, including the HEB. This model predicts an age for the oldest Emperor Seamounts that matches published ages, implying that a linear age-distance relationship might extend back to at least 82 Ma. In contrast, Hawaiian age progression was much faster since at least ~15 Ma and possibly as early as ~27 Ma. Linear age-distance relations for the Hawaii-Emperor and Louisville seamount chains predict ~300 km overall hotspot relative motion between 80 and 47.5 Ma, in broad agreement with numerical models of plumes in a convecting mantle, and paleomagnetic data We show that a change in hotspot relative motion may also have occurred between ~55 Ma and ~50 Ma. We interpret this change in hotspot motion as evidence that the HEB reflects a combination of hotspot and plate motion changes driven by the same plate/mantle reorganization.

Description: Phase equilibrium in the Ca-Mn-Sb-O system was studied in air at the temperature range from 1160 to 1250 °C and a pseudo-quaternary phase diagram for the system CaO-MnO-Mn 2 O 3 -Sb 2 O 5 is presented. The following compounds were discovered: new antimonate Ca 7 Sb 2 O 12 with a perovskite-like structure, solid solutions Mn 2– x Ca x Sb 2 O 7 (0 ≤ x ≤ 1.6) with a 3 T -weberite structure, and Ca 2– x Mn x Sb 2 O 7 (0 ≤ x ≤ 0.23) with a 2 O -weberite structure, as well as solid solutions Ca 2 Mn 1+ x Sb 1– x O 6 with monoclinic (0 ≤ x ≤ 0.67) and orthorhombic (0.75 ≤ x ≤ 1) perovskite structures. The existence of a number of double and ternary oxides and solid solutions on the basis of Sb 5+ and Mn 2+ , Mn 3+ , Mn 4+ and with mixed manganese valence is confirmed.

Description: The reaction of LAlMe 2 ( 1 ) [L = HC(CMeNAr) 2 , Ar = 2,6- i Pr 2 C 6 H 3 ] with diphenylstannanediol resulted in the methylalumoxane compound L(Me)Al(μ-O)Al(Me)L ( 3 ). Compound (LAlO) 2 B(2, 6-OCH 3 C 6 H 4 )(μ-O) ( 4 ) containing the Al 2 BO 3 six-membered ring was accomplished by reacting the precursor LAlH 2 ( 2 ) with 2,6-dimethoxyphenylboronic acid. The two compounds were characterized by 1 H NMR spectroscopy, elemental analysis, and single-crystal X-ray structural analysis.

Description: ABSTRACT Axial Seamount, an active submarine volcano on the Juan de Fuca Ridge at 46°N, 130°W, erupted in January 1998 along 11 km of its upper south rift zone. We use ship-based multibeam sonar, high-resolution (1-m) bathymetry, sidescan sonar imagery, and submersible dive observations to map four separate 1998 lava flows that were fed from eleven eruptive fissures. These new mapping results give an eruption volume of 31 x 10 6 m 3 , 70% of which was in the northern-most flow, 23% in the southern-most flow, and 7% in two smaller flows in between. We introduce the concept of map-scale submarine lava flow morphology (observed at a scale of 100s of meters, as revealed by the high-resolution bathymetry), and an interpretive model in which two map-scale morphologies are produced by high effusion-rate eruptions: “inflated lobate flows” are formed near eruptive vents, and where they drain downslope more than 0.5-1.0 km, they transition to “inflated pillow flows.” These two morphologies are observed on the 1998 lava flows at Axial. A third map-scale flow morphology that was not produced during this eruption, “pillow mounds,” is formed by low effusion-rate eruptions in which pillow lava piles up directly over the eruptive vents. Axial Seamount erupted again in April 2011 and there are remarkable similarities between the 1998 and 2011 eruptions, particularly the locations of eruptive vents and lava flow morphologies. Because the 2011 eruption reused most of the same eruptive fissures, 58% of the area of the 1998 lava flows is now covered by 2011 lava.

Description: A novel fairly stable N -trimethylsilylamino(dichloro)phosphine was prepared, in which the nitrogen atom bears a 9-borabicyclo[3.3.1]nonyl group. The gas phase structures of various amino- and silylaminophosphines including a phosphenium cation and an amino(imono)phosphine were optimized at the B3LYP/6-311+G(d, p) level of theory, and NMR parameters were calculated. Both magnitude and sign of the two-bond coupling constants 2 J ( 31 P, N, 13 C) and 2 J ( 31 P, N, 29 Si), known to be sensitive towards the respective conformation, are well reproduced by the calculations. This also holds for 1 J ( 31 P, 15 N), although calculated values 1 K ( 31 P, 15 N) (all 〈 0) are slightly more negative [ 1 J ( 31 P, 15 N) more positive] than experimental values.

Description: A new synthetic entry to iridium Keggin-type polyoxometalate complexes from [PW 11 O 39 ] 7– and K 3 [IrCl 6 ] under harsh conditions is reported. The complex [PW 11 O 39 IrCl] 5– ( 1 5– ) featuring an IrCl functionality was obtained in high yield and characterized by NMR spectroscopic and ESI-MS techniques. The presence of Li + (3–4 M) is essential for a quantitative yield of 1 5– . The reactivities of 1 5– and its rhodium analogue [PW 11 O 39 RhCl] 5– in ligand substitution at the noble metal site were studied. Thiocyanate coordination successfully yielded (Bu 4 N) 5 [PW 11 O 39 M (SCN)] [ M = Rh ( 2a ), Ir, ( 3a )]. In both cases, the SCN ligands are coordinated by sulfur atoms, according to 13 C NMR and IR spectroscopic data. Gas-phase fragmentation reactions of compounds 2a and 3a were also investigated by collision-induced dissociation (CID) experiments. Reaction of [PW 11 O 39 RhCl] 5– with NaN 3 resulted in Cl – to OH – replacement accompanied by the liberation of the RhCl fragment, whereas 1 5– proved unreactive with NaN 3 . Attempts to coordinate NO 2 – are adversely affected by competing noble metal excision with formation of free [PW 11 O 39 ] 7– .

Description: Four discrete metal-radical complexes, [Cu( p -MePh-COO) 2 (NITpPy) 2 ] ( 1 ), [Ni( m -MePhCOO) 2 (NITpPy) 2 (H 2 O) 2 ] · (CH 3 -OH) 2 ( 2 ), [Mn( p -MePhCOO) 2 (NITpPy) 2 (H 2 O) 2 ] ( 3 ), and [Mn( m -MePhCOO) 2 (NITpPy) 2 (H 2 O) 2 ] ( 4 ) [NITpPy = 2-(4-pyridyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxyl-3-oxide] were synthesized and characterized by elemental analyses, IR spectroscopy, PXRD, single-crystal X-ray diffraction, and magnetic susceptibility. For the four complexes, the crystal structural analyses indicate that the two radical ligands coordinated to the metal ions by the nitrogen atoms of the pyridine rings form three spin complexes, where toluates act as co-ligands. Weak antiferromagnetic interactions [ J Cu–Rad = –6.75 cm –1 ( 1 ), J Co–Rad = –4.15 cm –1 ( 2 ), J Mn–Rad = –0.22 cm –1 ( 3 ), and J Mn–Rad = –3.74 cm –1 ( 4 )] were observed, spin polarization mechanism and orbital symmetry are used to explain the magnetic coupling in these complexes.

Description: The new ternary compounds UP 2 S 6 , UP 2 S 7 , U(P 2 S 6 ) 2 , and U 3 (PS 4 ) 4 were prepared from uranium metal, phosphorus pentasulfide, and sulfur at 700 °C. The crystal structures were determined by single-crystal X-ray diffraction methods. UP 2 S 6 ( I ) crystallizes in the ZrP 2 S 6 structure type [tetragonal, P 4 2 / m , a = 6.8058(7) Å, c = 9.7597(14) Å, Z = 2], which consists of central uranium(IV) atoms coordinated by P 2 S 6 4– anions (staggered conformation). The anions are two-dimensional connectors for four uranium cations arranged in one plane. The structure of UP 2 S 7 ( II ) [orthorhombic, Fddd , a = 8.9966(15) Å, b = 15.2869(2) Å, c = 30.3195(5) Å, Z = 16] is closely related to the monoclinic ZrP 2 S 7 structure type. It consists of U 4+ cations linked by P 2 S 7 4– ligands, the resulting 3D network contains large pores (diameter approx. 3.5 × 16.7 Å). In the previously reported compound U(P 2 S 6 ) 2 ( III ) [ I 4 1 / a , a = 12.8776(9) Å, c = 9.8367(10) Å, Z = 2], the metal atoms are coordinated by four bidentate P 2 S 6 2– ligands. This arrangement can be considered as a pseudotetrahedral coordination of the uranium atoms by the linear ligands. Three of the resulting diamondoid frameworks are inseparably interwoven in order to optimize space filling. U 3 (PS 4 ) 4 ( IV ) [ I 4 1 / acd , a = 10.7440(9) Å, c = 19.0969(2) Å, Z = 2] crystallizes in a defect variant of the PrPS 4 structure type, with 50 % of the U2 sites statistically occupied with uranium atoms. The resulting stoichiometry is U 3 (PS 4 ) 4 with tetravalent uranium atoms. The structure of U 3 (PS 4 ) 4 consists of uranium atoms connected by PS 4 3– groups, each PS 4 group linking four central uranium atoms. Vibrational spectra, which were recorded for I – III , show good agreement between the obtained results and the expected values for the anionic units, while magnetic measurements confirm the presence of tetravalent uranium.

Description: A global map of surface heat flow is presented on a 2° by 2° equal area grid. It is based on a global heat flow data set of over 38,000 measurements. The map consists of three components. Firstly, in regions of young ocean crust (〈67.7Ma) the model estimate uses a half-space conduction model based on the age of the oceanic crust, since it is well known that raw data measurements are frequently influenced by significant hydrothermal circulation. Secondly in other regions of data coverage the estimate is based on data measurements. At the map resolution these two categories (young ocean, data covered) cover 65% of Earth's surface. Thirdly, for all other regions the estimate is based on the assumption that there is a correlation between heat-flow and geology. This assumption is assessed and the correlation is found to provide a minor improvement over assuming that heat flow would be represented by the global average. The map is made available digitally.

Description: We present 36 new 40 Ar- 39 Ar incremental heating age determinations from the Caribbean Large Igneous Province (CLIP) providing evidence for extended periods of volcanic activity and suggest a new tectonomagmatic model for the province's timing and construction. These new 40 Ar- 39 Ar ages for the Curaçao Lava Formation (CLF) and Haiti's Dumisseau Formation show evidence for active CLIP volcanism from 94 to 63 Ma. No clear changes in geochemical character are evident over this period. The CLF has trace element signatures (e.g., Zr/Nb = 10-20) and flat rare earth element (REE) trends consistent with plume volcanism. The Dumisseau Formation also has plume-like geochemistry and steeper REE trends similar to ocean island basalts. Volcanism in the Dumisseau Formation appears to have largely ceased by 83 Ma while at Curaçao it continued until 63 Ma. A rapidly surfacing and melting plume head alone does not fit this age distribution. Instead, we propose that the residual Galapagos plume head, following initial ocean plateau construction, was advected eastward by asthenospheric flow induced by subducting oceanic lithosphere. Slab rollback at the Lesser Antilles and Central America subduction zones created an extensional regime within the Caribbean plate. Mixing of plume with upwelling asthenospheric mantle provided a source for intermittent melting and eruption through the original plateau over a ~30 Ma period.

Description: 2-Pivaloylpterin, an acylated derivative of the biochemically relevant pterin [2-amino-4-oxo-(3 H )pteridine] heterocyclus, undergoes stepwise metallation by the 1, 1′-bis(diphenylphosphanyl)ferrocene-copper(I) cation, [(dppf)Cu] + . The final product obtained, [Cu 3 (dppf)(μ 2 -dppf)(PP)(PP-H + )] 2 (BF 4 ) 4 , could be structurally characterized to reveal coordinative saturation with binding of central Cu + ions to N 1 ,N 3 ,O 4 ,N 5 ,N 8 and pivaloyl-O donor atoms.

Description: Abstract . Two coordination polymers, namely, {[Cd(cdpc)(hmt)(H 2 O)] · H 2 O} n ( 1 ), and [Mn(Hcdpc) 2 (4, 4′-bpy)(H 2 O)] n ( 2 ), were constructed by synergistic assembly through the mixed-ligand synthetic strategy (H 2 cdpc = 1-carboxymethyl-3, 5-dimethyl-1H-pyrazole-4-carboxylic acid, hmt = hexamethylenetetramine, and 4, 4′-bpy = 4, 4′-dipyridine). Their structures were determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR spectra, powder X-ray diffraction (PXRD), and thermogravimetric (TG) analyses. Single X-ray diffraction analysis reveals that complex 1 is a 2D 4-connected sql sheet, and complex 2 is an interesting 1D loop chain. The two complexes are further expanded to 3D supramolecular structure through non-covalent bonds. Besides, luminescent properties of two complexes in the solid state and magnetic property of 2 were also investigated.

Description: The chemical preparation, structure, luminescence, and electronic properties are given for a new potassium holmium cyclotetraphosphate KHoP 4 O 12 , a promising optics material for applications. Single-crystal X-ray diffraction analysis shows that the newly synthesized compound crystallizes in the monoclinic system with space group C 2/ c and Z = 4. [P 4 O 12 ] 4– anionic rings and HoO 8 polyhedra display a three-dimensional (3D) framework by corner-sharing. The ten-coordinated potassium atoms are located in the delimited tunnels. KHoP 4 O 12 exhibits the blue light emission under the excitation of 330 nm. To gain further insights into electronic properties of crystal KHoP 4 O 12 , theoretical calculation based on density functional theory (DFT) was performed using the total-energy code CASTEP with the LDA + U approach. The calculated bandgap with U = 3.0–3.5 eV is in good agreement with the experimental measurement.

Description: The facile synthesis, molecular structure, and reactivity of [Cu(C 7 H 7 NH 2 )Cl] 4 ( 1 ) towards dioxygen and derivatives is reported. The compound could easily be prepared in good yields by mixing CuCl and benzylamine under inert conditions in dichloromethane. Surprisingly this copper(I) compound, a copper(I) tetramer with Cu I ··· Cu I interactions of 2.89 Å, was formed instead of an expected cubane cluster. Oxidation reactions led to formation of μ-oxido-species as intermediates, however 1 did not show any catalytic activity in the activation of CH bonds. In contrast it turned out that 1 was quite stable towards oxidation. Analogous reactions with CuBr or CuI were different and neither cluster units or polynuclear copper(I) complexes were obtained.