1,1-Dithiooxalsäurederivate als Liganden in Übergangsmetallkomplexen: Struktur von O-Methyl-1,1-dithiooxalato-bis(triphenylphosphin)kupfer(I) und -silber(I)

1,1-Dithiooxalic Acid Derivatives as Ligands in Transition Metal Complexes: Structure of O-Methyl-1,1-dithiooxalato-bis(triphenylphosphine)copper(I) and silver(I) Despite O-Alkyl-1,1-dithiooxalates are also tetradentate thioligands their tendency towards the formation of multi-nuclear bridged chelates as found for the basic 1,1-dithiooxalate does practically not exist because of derivatisation. The reaction with triphenylposphinemetal(I)-halogenides yields defined mono-nuclear mixed ligand complexes: O-Methyl-1,1-dithiooxalato-bis(triphenylphosphine)copper(I) ( 2 ) and silver(I) ( 1 ). X-ray analysis shows that both complexes ( 1 and 2 ) are isostructural and crystallize in the monoclinic space group P2₁/n: (Ph₃P)₂Ag(S₂C₂O₂Me) ( 1 ) with a = 12.794(1), b = 21.314(4), c = 13.560(1) Å, β = 97.983(6)°, and (Ph₃P)₂Cu(S₂C₂O₂Me) ( 2 ) with a = 12.622(1), b = 21.196(2), c = 13.426(1) Å, β = 96.533(7)°. These complexes are the first authentic examples of exclusively end-on coordinated thiooxalate.     

The Suitability and Usage of 18O and Chloride as Natural Tracers for Bank Filtrate at the Middle River Elbe

Abstract

Flow times and infiltration behaviour are very important for water extraction from riverbank filtration. Both the chloride content and the isotopic composition of oxygen (δ¹⁸O) were found to be suitable indicators for the conditions encountered in the middle course of the River Elbe near Torgau. The ranges for Elbe water were measured to be 20–43 mg Cl/l (1995-97) and -11 to -8.5‰ δ¹⁸O (1993-97). Both methods permitted flow-time spectra at two adjacent sampling profiles incorporating river and production wells to be obtained, indicating the preferred flow paths and the vertical extension of the riverbank filtrate plume in the aquifer. However, since the differences between the mean values for river water and regional groundwater were too small the percentage of river water abstracted from production wells could not be calculated.     

Stable Isotope Geochemistry of Antarctic Salt Efflorescences

Salt efflorescences consisting of gypsum sampled mainly in the Schirmacher Oasis have been analyzed for the isotopic composition of the water of crystallization and of the sulphate-sulphur. For comparison, a few samples from other Antarctic locations (Guettard Range, Prince Charles Mts., Insel Mts.) were included in the study. The isotopic variations of the water of crystallization of secondary gypsum and the calculated isotopic composition of the mother solution reflect the local climatic conditions during the precipitation of the efflorescences. It is therefore possible to obtain qualitative information about the climatic conditions prevailing in the studied region.     

Sulphur and oxygen isotopic characters of dissolved sulphate in groundwater from the Pleistocene aquifer in the southern Jordan Valley (Jericho area,Palestine)

Sulphate and chloride concentrations in the shallow Pleistocene aquifer systems in the lower Jordan valley area indicate a general trend of increasing salinity eastward and southward. This study was conducted in one of the important sub-basins feeding the Pleo–Pleistocene aquifer in the Jericho area in the southern part of the valley using S and O isotopes of dissolved sulphate. The results show that sulphate has mainly two contributions to the groundwater. One is the surface seepage, which is present as a salty leachate form with the positive δ³⁴S_sulphate values of primary gypsum in Lisan and Samara formations, and the second is the upwelling saline water which was in contact with a deep secondary gypsum, aragonites and salty rocks and rose up under heavy abstraction with depleted ³⁴S in sulphate and relatively high sulphate and chloride content. The latest was clearly shown in the Arab Project wells to the east that is undergoing a continuous heavy abstraction. The isotopic signatures of S and O in these wells to the east show that this depleted ³⁴S and highly concentrated sulphate might also indicate a dissolved sulphate originating from pyrite oxidation that results from the interaction with a pyrite-rich aquifer, which can well up with salty water under heavy abstraction and is oxidised in the upper aerobic shallow aquifer.     

Vinyl Triflimides—A Case of Assisted Vinyl Cation Formation

A new concept for selectivity control in carbocation‐driven reactions has been identified which allows for the chemo‐, regio‐, and stereoselective addition of nucleophiles to alkynes—assisted vinyl cation formation—enabled by a Li⁺‐based supramolecular framework. Mechanistic analysis of a model complex (Li₂NTf₂⁺?3 H₂O) confirms that solely the formation of a complex between the incoming nucleophile and the transition state of the alkyne protonation is responsible for the resulting selective N addition to the vinyl cation. Into the bargain, a general, operationally simple synthetic procedure to previously inaccessible vinyl triflimides is provided.     

Heat transfer and mass transport in a multiwafer MOVPE reactor: modelling and experimental studies

An improved detailed model for the calculation of the temperature distribution in a multiwafer Planetary Reactor™ has been developed. The temperature field of the reactor has been calculated in dependence of the reactor parameters for (Al,Ga)As growth as well as on the kind and the thickness of the wall and susceptor deposits. The amount of parasitic wall deposits can be minimized by a proper tuning of the reactor temperature distribution. Calculated GaAs growth rate profiles on 3 inch wafers show a strong dependence on the temperature field in the reactor and the amount of parasitic deposits. These predicted relationships have been used to optimize the reactor temperature distribution in order to minimize parasitic wall depositions. By this procedure a growth rate uniformity of < 1% on 3 inch wafers can be reproducibly achieved.     

Synthesis, EPR spectrum and X-ray structure of tetra-n-butylammonium bis(benzene-1,2-dithiolato(2−)-κS,S′)platinate(III)

The new salt, tetra-n-butylammonium bis(benzene-1,2-dithiolato(2−)-κ²S,S′)platinate(III), [NBu₄][Pt(C₆H₄S₂)₂] (1), has been synthesized in ethanol/water, and fully characterized by single crystal X-ray structure determination. The central platinum in the complex ion [Pt(bdt)₂]⁻ is tetracoordinated by the S atoms of the bdt²⁻ ligands (bdt²⁻ is benzene-1,2-dithiolate) in a square-planar geometry. The well-resolved frozen solution EPR spectrum exhibits rhombic symmetry. The room temperature effective magnetic moment (μ_eff = 1.80 Bohr magneton) is in line with this spectrum and strongly supports the Pt(III) oxidation state in 1. This observation is in excellent agreement with previous results reported on closely related Ni(III), Pd(III) and Pt(III) species.     

Contributions of the different water sources to the Elqui river runoff (northern Chile) evaluated by H/O isotopes

We present the results of an isotope (2H and 18O) and hydrogeochemical study in order to constrain the origin, recharge, and evolution of the surface and groundwater in the arid Andean realm of the Elqui watershed. The results of 2H and18O analyses of water samples obtained during our summer and winter campaigns indicate a generally meteoric origin of the river and spring waters of the watershed. The isotope signature of water of the Elqui river and its tributaries as well as that of groundwater in the coastal region fits the 2H-18O relation of delta2H =7.61delta18O+6.1. A relatively fast discharge and a quasi-closed catchment area can be asserted for water along the river flow path. The tributaries from the more arid coastal area, north of the Elqui river, differ in their isotopic signature due to evaporation and hydrochemically due to interactions with the strongly altered and fractured volcanic rocks of the basement. In the Andean zone, the18O-enriched hydrothermal spring of Ba?os del Toro exhibits the influence of water-rock interaction processes. The chemistry of the river water changes from sulphate- to chloride-rich along the river course from the high Andean mountains to the coast. The sulphate-rich character of these Andean waters reflects their passage through sulphide-rich rock massifs that were subjected to strong oxidation processes in the near superficial environment. This sulphate signature is enforced by past and present mining of precious metal epithermal deposits (e.g. those of El Indio-Tambo Au-Cu-As district), in which mineralised zones were developed during a series of Miocene magmatic-hydrothermal episodes in the Andean realm. Owing to the proximity of the lower Elqui river waters and its tributaries to the Pacific coast, the chloride character may be induced by agricultural and marine (sea spray, fog) sources. Generally, the main source of the Elqui river water is mainly attributed to surface runoff and less to contributions from the basement fractured aquifer.     

Sulphur and oxygen isotopic characters of dissolved sulphate in groundwater from the Pleistocene aquifer in the southern Jordan Valley (Jericho area, Palestine)

Sulphate and chloride concentrations in the shallow Pleistocene aquifer systems in the lower Jordan valley area indicate a general trend of increasing salinity eastward and southward. This study was conducted in one of the important sub-basins feeding the Pleo-Pleistocene aquifer in the Jericho area in the southern part of the valley using S and O isotopes of dissolved sulphate. The results show that sulphate has mainly two contributions to the groundwater. One is the surface seepage, which is present as a salty leachate form with the positive delta34Ssulphate values of primary gypsum in Lisan and Samara formations, and the second is the upwelling saline water which was in contact with a deep secondary gypsum, aragonites and salty rocks and rose up under heavy abstraction with depleted 34S in sulphate and relatively high sulphate and chloride content. The latest was clearly shown in the Arab Project wells to the east that is undergoing a continuous heavy abstraction. The isotopic signatures of S and O in these wells to the east show that this depleted 34S and highly concentrated sulphate might also indicate a dissolved sulphate originating from pyrite oxidation that results from the interaction with a pyrite-rich aquifer, which can well up with salty water under heavy abstraction and is oxidised in the upper aerobic shallow aquifer.