Crystal structure of form 1, magnetic properties and polymorphism of bis (NN-di-(n-propyl)dithiocarbamato iron (III) iodide

The crystal structure of bis (NN-di(n-propyl)dithiocarbamato iron(III) iodide, Fe^III(S₂CN₆H₁₄)₂I, has been determined by the heavy-atom method and refined toR=0.055 for 3487 reflections withI(hkl)>3I(hkl). The crystals are triclinic,C¯1,Z=8,a=27.644(6),b=19.186(4),c=8.694(2) Å,=87.79(1),=88.72(1), =101.87(2)°. The I-Fe bond lengths are different in the two moleculesA andB in the asymmetric unit, having values of 2.642 Å (2.655) and 2.612 Å (2.634) respectively (libration-corrected values given in parentheses). The measured effective magnetic moment _eff3.89 BM, independent of temperature (93-353K), suggests a spinS of 3/2 with three unpaired electrons for Fe^III.     

Synthesis,Structure, Bonding,and Reactivity of Metal Complexes Comprising Diborane(4) and Diborene(2): [{Cp*Mo(CO)2}2{μ‐η2:η2‐B2H4}] and [{Cp*M(CO)2}2B2H2M(CO)4], M=Mo,W

The reaction of [(Cp*Mo)₂(μ‐Cl)₂B₂H₆] ( 1 ) with CO at room temperature led to the formation of the highly fluxional species [{Cp*Mo(CO)₂}₂{μ‐η²:η²‐B₂H₄}] ( 2 ). Compound 2, to the best of our knowledge, is the first example of a bimetallic diborane(4) conforming to a singly bridged C_s structure. Theoretical studies show that 2 mimics the Cotton dimolybdenum–alkyne complex [{CpMo(CO)₂}₂C₂H₂]. In an attempt to replace two hydrogen atoms of diborane(4) in 2 with a 2e [W(CO)₄] fragment, [{Cp*Mo(CO)₂}₂ B₂H₂W(CO)₄] ( 3 ) was isolated upon treatment with [W(CO)₅?thf]. Compound 3 shows the intriguing presence of [B₂H₂] with a short B?B length of 1.624(4) Å. We isolated the tungsten analogues of 3 , [{Cp*W(CO)₂}₂B₂H₂W(CO)₄] ( 4 ) and [{Cp*W(CO)₂}₂B₂H₂Mo(CO)₄] ( 5 ), which provided direct proof of the existence of the tungsten analogue of 2 .     

Application of self-organizing maps for the classification of chromatographic systems and prediction of values of chromatographic quantities

The separation of a complex mixture of inorganic and organic anions by ion chromatography–capillary electrophoresis using a cationic polymer added to the background electrolyte and indirect UV detection has been studied. The addition of unmodified polymer to an electrolyte suitable for indirect detection resulted in the appearance of a system peak due to the counter-anion on the polymer and while the position of the analytes relative to this system peak could be changed, this was found to be an unacceptable approach for mixtures of large numbers of analytes. Although conversion of the polymer to replace the counter-ion with the indirect UV detection probe ion simplified the system, this approach restricted the flexibility of the system because the probe and polymer concentration were necessarily linked. This limitation could be overcome by selecting the appropriate type of probe ion, with probes having a low ion-exchange selectivity coefficient providing greater retention of analytes than probes with a high ion-exchange selectivity coefficient. Three electrolyte systems with different probes (benzoate, chromate and phthalate) were modelled using a previously derived migration equation and this was used to optimise the electrolyte composition to enable the separation of a mixture of 24 inorganic and organic anions within 7 min. The electrolyte composition was then optimised for the analysis of anions in Bayer liquor with the final separation selectivity being substantially improved for selected key analytes.     

Ion Association and Solvation Behavior of Some 1-1 Electrolytes in 2-Ethoxyethanol Probed by a Conductometric Study

Precise measurements of the electrical conductances of solutions of potassium thiocyanate (KCNS), ammonium thiocyanate (NH₄CNS), sodium nitrate (NaNO₃) and ammonium nitrate (NH₄NO₃) in 2-ethoxyethanol (EE) at temperatures 35, 40, 45 and 50,^∘C are reported. The conductance data have been analyzed by the 1978 Fuoss conductance equation. A thermodynamic analysis of the ionic association processes has also been made and the Coulombic forces are found to play a major role in the association processes. The ionic contributions to the limiting equivalent conductances have been determined using the reference electrolyte method. Strong association was found for all these electrolytes in this solvent medium. The cations are found to be substantially solvated in 2-ethoxyethanol, whereas the anions appear to have only weak interaction with the solvent molecules.     

Neutron diffraction experiments on CsCrI3 at 300, 77, and 1.2°K: H. W. Zandbergen and D. J. W. Ijdo. Gorlaeus Laboratories,University of Leiden,P.O. Box 9502, 2300 RA Leiden,The Netherlands

The orthorhombic α-PbO₂ phase of FeNbO₄ was prepared and its photoelectronic properties measured: Sintered disks were shown to be n type and gave a resistivity of 40 Ω-cm. Measurements of the photoresponse gave a flat-band potential between 0.1 and 0.4 V vs SCE at a pH of 8.5 and an optical band gap of 2.08(2) eV. Several higher-energy band gaps at 2.68(2), 2.94(2), 3.24(2), and 4.38(2) eV were also determined. There appears to be an enhancement of the quantum efficiency due to the presence of [FeO₆] active centers while retaining the fundamental characteristics of the [NbO₆] octahedra.     

Mixed-ligand complexes of osmium(III)/(IV) 8-quinolinolates: synthesis,characterization and redox behaviour

Summary A group of mixed-tris chelates of osmium(III) and osmium(IV) of type [OsAQ₂]^{0/1 +} [HA = glycine (glyH), picolinic acid (PicH) and quinaldic acid (qndH); HQ = 8-quinolinol] were prepared and characterized by physicochemical, magnetic and spectroscopic methods. The complexes exhibit several spin-allowed and spin-forbidden absorption bands and shoulders in the 200–700 nm region. The new chelates are electroactive and display nearly reversible Os^IV-Os^III and Os^III-Os^II couples in the ca. –1.1 to +0.3 V range versus s.c.e. The stability of metal oxidation states is discussed in terms of the electrochemical results.     

An all-optical integrated system for implementing arithmetic operation in 2’s complement method with the active participation of non-linear material based switches

Optics is regarded undoubtedly a potential and successful candidate in information and data processing because of its inherent parallelism. In last few decades several all-optical data processors, algebraic processors, arithmetic processors are proposed. Here in this communication the authors propose a completely new scheme for implementing binary data arithmetic in 2’s Complement method which is the most advantageous among all other established subtraction methods. To implement it we use non-linear material massively.     

Conductance of Some 1:1 Electrolytes in N,N-Dimethylacetamide at 25°C

Precise conductance measurements of solutions of lithium chloride, lithium bromide, lithium iodide, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluoroarsenate, tetrabutylammonium bromide, and tetrabutylammonium tetraphenylborate in N,N-dimethylacetamide are reported at 25°C in the concentration range 0.005–0.015 mol-dm^–3. The conductance data have been analyzed by the 1978 Fuoss conductance equation in terms of the limiting molar conductance (⁰), the association constant (K _a), and the association diameter (R). The limiting ionic conductances have been estimated from an appropriate division of the limiting molar conductivity of the reference electrolyte Bu₄NBPh₄. Slight ionic association was found for all these salts in this solvent medium. The results further indicate significant solvation of Li⁺ion, while the other ions are found to be unsolvated in N,N-dimethylacetamide.