Über Chalkogenidhalogenide des Chroms Synthese,Kristallstruktur und Magnetismus von Chromsulfidbromid,CrSBr

Chalkogenidehalides of Chromium. Synthesis, Crystal Structure, and Magnetism of Chromiumsulfidebromide, CrSBr CrSBr is obtained from chromium metal and S₂Br₂ in a sealed quartz ampoule at 880°C. It forms air stable, black crystals. The crystal structure determination (space group Pmmn, lattice constants a = 476.7(2), b = 350.6(2), c = 796.5(4) pm, Z = 2, R = 0.026) shows, that CrSBr crystallizes in the FeOCl structure type. The structure consists of layers which are stacked perpendicular to the c axis. The layers are formed by distorted, edge sharing CrS₄Br₂ octahedra. The interatomic distances are Cr? S 239.7 and 241.5 pm, Cr? Br 249.4 pm. To explain the unusual temperature factor of the Br atom the structure determination was additionaly carried out at 205 K and 118 K. A linear decrease of the coefficients of the anisotropic temperature factors of all atoms was found. The coefficients can be extrapolated to zero for 0 K. This shows the large displacement parameter U₁₁ of the Br atom to be caused by thermal vibrations. Even under forced conditions CrSBr does not form intercalation compounds with pyridine or tetracyanoethylene. CrSBr shows a marked antiferromagnetic behavior with a Néel temperature of 132 K and a critical field of 0.35 Tesla at 4.2 K.     

Electrocatalytic Proton Reduction by a Cobalt Complex Containing a Proton-Responsive Bis(alkylimdazole)methane Ligand: Involvement of a C−H Bond in H2 Formation

Homogeneous electrocatalytic proton reduction is reported using cobalt complex [ 1 ](BF₄)₂. This complex comprises two bis(1-methyl-4,5-diphenyl-1H-imidazol-2-yl)methane (HBMIM ) ligands that contain an acidic methylene moiety in their backbone. Upon reduction of [ 1 ](BF₄)₂ by either electrochemical or chemical means, one of its HBMIM ligands undergoes deprotonation under the formation of dihydrogen. Addition of a mild proton source (acetic acid) to deprotonated complex [ 2 ](BF₄) regenerates protonated complex [ 1 ](BF₄)₂. In presence of acetic acid in acetonitrile solvent [ 1 ](BF₄)₂ shows electrocatalytic proton reduction with a k_obs of ≈200 s⁻¹ at an overpotential of 590 mV. Mechanistic investigations supported by DFT (BP86) suggest that dihydrogen formation takes place in an intramolecular fashion through the participation of a methylene C−H bond of the HBMIM ligand and a Co^II−H bond through formal heterolytic splitting of the latter. These findings are of interest to the development of responsive ligands for molecular (base)metal (electro)catalysis.     

Luminescence temperature antiquenching of water-soluble CdTe quantum dots: role of the solvent

Luminescence temperature antiquenching (LTAQ) is observed for water-soluble CdTe quantum dots (QDs) capped with aminoethanethiol (AET). The efficient exciton emission (quantum efficiency of approximately 40% at 300 K) is quenched almost completely as the QD solutions are cooled to below 230 K and is fully recovered around 270 K upon warming up to room temperature (LTAQ). Temperature-dependent lifetime measurements show that the quenching rate is high, resulting in an on/off behavior. No LTAQ is observed for CdTe QDs capped with aminoundecanethiol (AUT). The LTAQ is explained by the influence of solvent freezing on the surface of the QD core. Freezing of the solvation water molecules surrounding the QD will induce strain in the capping shell, due to the interaction between water and the charged heads of the capping molecules. Short carbon chains (AET) will propagate the strain to the QD surface, creating surface quenching states, whereas long and flexible chains (AUT) will dissipate the strain, thus avoiding surface distortion. Freezing-point depression by the addition of methanol results in a lowering of the transition temperature. Additional support is provided by the size dependence of the LTAQ: smaller particles, with higher local ionic strength due to a higher density of charged NH(3)(+) surface groups, experience a lower transition temperature due to stronger local freezing-point depression.     

Pyrolysis studies of aromatic polyesters

The products of pyrolysis, at 400°C in vacuo (1 Pa), of poly(ethyleneterephthalate) (PET) and poly(butyleneterephthalate) (PBT) were studied. The products were identified by gas chromatography/mass spectrometry technique. The highly volatile products of PET contained acetaldehyde, benzene, toluene, styrene and ethylbenzene and in the case of PBT, butadiene, tetrahydrofuran, vinylcyclohexene and ethylbenzene were the major products. A qualitative analysis of the products of low volatility revealed that the main components were benzoic acid, terephthalic acid, monovinyl esters of terephthalic acid and higher oligomers in the case of PET, whereas benzoic acid, monobutenyl esters of terephthalic acid and higher oligomers were the main products from PBT. The results obtained were in good agreement with those obtained from pyrolysis experiments, carried out directly in the mass spectrometer. Mechanisms to explain the occurrence of the different products are proposed.     

One-dimensional magnetism and crystal structure ofcatena-di-bromobis(3,5-dimethylpyridine)copper(II)

Summary Crystals ofcatena-di--bromobis(3,5-dimethylpyridine)copper(II) are monoclinic, space group P2₁/a. The unit cell constants area=13.900(2),b=14.416(2),c=4.097(1) Å,=93.49(2)°, V=819.4 ų and Z=2. The structure was determined from powder data using a Guinier-Johansson focussing powder camera. The structure was solved using a simplex method for function minimization to a conventional R-value of 0.13.The structure consists of infinite linear chains parallel toc in which the copper coordination is distorted elongated octahedral. Cu-Br distances were found to be 2.449(7) and 3.286(7) Å, whereas the Cu-N bond length is 2.02(2) Å. All distances are in the range usually observed for this type of compounds.The antiferromagnetic superexchange interactions between adjacent Cu^II ions (J = –21 cm^–1) has been compared with those observed in structural similar CuBr₂L₂ compounds. The differences in observed J-values are discussed briefly, in relation to the structural variations. It appears that very small changes in structural parameters strongly affect the magnetic exchange.     

The discovery of two kinds of ion pairs

The discovery and implications of the existence of two kinds of ion pairs in solutions of carbanion salts is described. Also discussed are the factors controlling tight–loose ion pair equilibrium: the nature of the carbanion and its counterion, temperature, pressure, solvent, and cation‐complexing additives. A few examples are presented of the effect of these ionic species on the mechanisms of anionic polymerization and proton transfer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3655–3667, 2004     

Ueber die Titration der Schwefels?ure mit Benzidinchlorhydrat

Zusammenfassung In Vorstehendem wurde zunächst die Ausführung der von einem von uns ausgearbeiteten Schwefelsäuretitration mittelst Benzidinchlorhydrats nochmals genau beschrieben, sodann wurden die Bedingungen festgestellt, unter denen verschiedene Schwefelsäuremengen am genauesten zu bestimmen waren. Es hat sich dabei herausgestellt, dass die Schwefelsäure bis zu 0,01g H₂SO₄ herunter nach der beshriebenen Methode auf 1–2 genau bestimmt werden kann. Die Anwendung der Methode auf verschiedene Fälle (Ammoniumsulfat, Alaun, Zinksulfat-heptahydrat, Mohr'sches Salz, Mangansulfat-tetrahydrat), wobei die Metalle in einigen Fällen vorher ausgefällt wurden, bestätigten die zuvor festgestellten Regeln; ausserdem wurde gezeigt, dass beim Ausfällen von Zink, Eisen und Mangan nach dem angegebenen Verfahren Schwefelsäure nicht mitgerissen wird. Die Zeit, welche eine derartige Bestimmung, auch wenn die beschriebenen Ausfällungen vorgenommen werden müssen, bei einiger Uebung erfordert, ist sehr kurz, weil alles Auswaschen und so weiter in Fortfall kommt, so dass auch hier ein Vortheil gegenüber dem gewichtsanalytischen Verfahren vorhanden ist.     

Insight into the extractability of metals from soils using an implementation of the linear adsorption isotherm model

This paper deals with an often overlooked artifact in sequential and single extraction of metals from soils, viz. the volume to mass (V/m) ratio as a potential source for inadequate extraction yields. We offer a theoretical framework to get a grip on this intricate parameter and came up with a model based on a linear adsorption isotherm to derive the correct maximal metal extractability for a certain extractant. We verified the model experimentally using 0.1 mol l⁻¹ nitric acid for extraction of seven metals (Cr, Co, Cu, Cd, Pb, Ni and Zn) from an urban soil sample, and concluded that commonly used V/m ratios in the range of 10-40 ml g⁻¹ may give as much as 50% too low extraction yields. Thus, a strong caveat is in place as to be very critical what V/m ratios to use and preferably apply the model derived to obtain the correct maximal extractability using a variable V/m ratio method.     

Über grünes Bis-(2-Iminoisopropyl-thiophenolato)-nickel(II) und weitere, ähnliche NiII-Komplexe

Green Bis-(2-iminoisopropyl-thiophenolato)nickel(II) and other Similar Ni^II Complexes The compounds [Ni^II(iitp)₂] 1 (iitp = 2-iminoisopropyl-thiophenolate), [Ni(imptp)₂] · 2 CH₃OH 2 , a dinuclear compound with an Ni? Ni distance of 276 pm, and [PPh₄] · [Ni^II(imptp)(SCN)] 3 (imptp = 2-(2-iminopentane-4-on)-thiophenolate) have been prepared by the reaction of nickel(II)-acetate-tetrahydrate with 2-iminoisopropyl-thiophenole and 2-(2-iminopentane-4-on)-thiophenole in methanol, respectively. They have been characterized by single-crystal X-ray structure analysis and other physical methods. The redox behaviour of 1–3 has been studied in detail (chemically as well as by cyclovoltammetry and ESR spectroscopy). Particularly interesting are the electronic properties of 1 and its reduction with NaBH₄ and the following reaction of the product with O₂. The complexes are model compounds for some Ni-containing enzymes. For details of the crystal structure determination see “Inhaltsübersicht”.     

Nitrogen binding to the FeMo-cofactor of nitrogenase

Density functional calculations are presented to unravel the first steps of nitrogen fixation of nitrogenase. The individual steps leading from the resting state to nitrogen binding at the FeMo-cofactor with a central nitrogen ligand are characterized. The calculations indicate that the Fe-Mo cage opens as dinitrogen binds to the cluster. In the resting state, the central cage is overall neutral. Electrons and protons are transferred in an alternating manner. Upon dinitrogen binding, one protonated sulfur bridge is broken. An axial and a bridged binding mode of dinitrogen have been identified. Adsorption at the Mo site has been investigated but appears to be less favorable than binding at Fe sites.