The dithiolene ligand and tetrathiafulvalene precursor molecules 4,5‐bis(bromomethyl)‐1,3‐dithiol‐2‐one and 4,5‐bis[(dihydroxyphosphoryl)methyl]‐1,3‐dithiol‐2‐one

The crystal structures of 4,5‐bis(bromomethyl)‐1,3‐dithiol‐2‐one, C₅H₄Br₂OS₂, (I), and 4,5‐bis[(dihydroxyphosphoryl)methyl]‐1,3‐dithiol‐2‐one, C₅H₈O₇P₂S₂, (II), occur with similar unit cells in the same monoclinic space group. Both molecules reside on a twofold symmetry axis coincident with the C=O bond, so that the substituents in the 4‐ and 5‐positions project above and below the plane of the 1,3‐dithiol‐2‐one ring. In both structures, the molecules align themselves in a head‐to‐tail fashion along the b axis, and these rows of molecules then stack, with alternating directionality, along the c axis. For (II), an extensive network of intermolecular hydrogen bonds occurs between molecules within the same stack and between adjacent stacks. Each –CH₂P(O)(OH)₂ group participates in four hydrogen bonds, twice as donor and twice as acceptor.     

Oxovanadium(IV)‐Salen Ion Catalyzed H2O2 Oxidation of Tertiary Amines to N‐Oxides– Critical Role of Acetate Ion as External Axial Ligand

The oxovanadium(IV)‐salen ion catalyzed H₂O₂ oxidation of N,N‐dimethylaniline forms N‐oxide as the product of the reaction. The reaction follows Michaelis–Menten kinetics and the rate of the reaction is accelerated by electron donating groups present in the substrate as well as in the salen ligand. This peculiar substituent effect is accounted for in terms of rate determining bond formation between peroxo bond of the oxidant and the N‐atom of the substrate in the transition state. Trichloroacetic acid (TCA) shifts the λ_max value of the oxidant to the red region and catalyzes reaction enormously. The cleavage of N? O bond by vanadium complex leads to moderate yield of the product. But the percentage yield of the product becomes excellent in the presence of TCA.     

Suppression of electron correlations in the superconducting alloys of Rh17−xIrxS15

We have studied the effect of Iridium doping (Rh_17?xIr_xS₁₅) in the rhodium sites of the strongly correlated superconductor Rh₁₇S₁₅. Even at low levels of doping (x = 1 and 2) we see a drastic change in the superconducting properties as compared to those of the undoped system. We deduce that there is a reduction in the density of states at the Fermi level from reduced Pauli susceptibility and Sommerfeld coefficient in the doped samples. Moreover, the second magnetization peak in the isothermal magnetization scan (‘fishtail’) which was very prominent in the magnetization data of the undoped crystal is suppressed in the doped samples. The temperature dependence of resistivity of the doped crystals show a remarkably different behavior from that of the undoped crystal with the appearance of a minima at lower temperatures, the position of which is fairly constant at different fields. Our data supports the notion that Iridium, which is a bigger atom than rhodium expands the lattice thereby, reduces the electron correlations that existed due to the interaction between closer lying rhodium atoms in the undoped system.     

Allocating flexible servers in serial systems with switching costs

Consider a firm that operates a make-to-order serial production system and employs a cross-trained workforce. We model such a firm as a tandem queuing system in which flexible servers can be allocated across stations, and assume that a switching cost is charged when servers move between stations. We show that even in the two-station two-server case the optimal policy follows a complex state-dependent structure that may be difficult to implement in practice. We propose three alternate heuristic policies and assess their performance. We show that a simpler policy which only moves one server can achieve close to optimal results.     

From ribbons to nanodot arrays: nanopattern design through reductive annealing

A new approach to the generation of nanoparticle arrays in periodic as well as non-periodic fashions has been discovered based on reduction of oxidized nanoscroll/nanoribbon precursors in the transmission electron microscope (carbothermal reduction) or by hydrogen annealing. Arrays consisting of nickel arsenide nanoparticles of size 3-4 nm have been generated.     

The revised generalized Tikhonov method for the backward time-fractional diffusion equation

In this paper, we solve the backward problem for a time-fractional diffusion equation with variable coefficients in a bounded domain by using the revised generalized Tikhonov regularization method. Convergence estimates under an a-priori and a-posteriori regularization parameter choice rules are given. Numerical example shows that the proposed method is effective and stable.     

Inclusion of temperature dependent shell corrections in Landau theory for hot rotating nuclei

Landau theory used for studying hot rotating nuclei usually uses zero temperature Strutinsky smoothed total energy for the temperature dependent shell corrections. This is replaced in this work by the temperature dependent Strutinsky smoothed free energy. Our results show that this replacement has only marginal effect for temperatures greater than 1 MeV but plays significant role at lower temperatures.     

Binuclear Ru(III) Schiff base complexes: synthesis,spectral characterization,oxidation, C?C coupling reactions and antibacterial activities

New hexa‐coordinated binuclear Ru(III) Schiff base complexes of the type {[(B)₂X₂Ru]₂L} (where B = PPh₃ or AsPh₃; X = Cl or Br; L = binucleating N₂O₂ Schiff bases) were synthesized and characterized by elemental analysis, magnetic susceptibility measurement, FT‐IR, UV–vis, ¹³C{¹H}‐NMR, ESR at 300 and 77 K, cyclic voltammetric technique, powder X‐ray diffraction pattern and SEM. The new complexes were used as catalysts in phenyl–phenyl coupling reaction and the oxidation of alcohols to their corresponding carbonyl compounds using molecular oxygen atmosphere at room temperature. Further, the new Schiff base ligands and their Ru(III) complexes were also screened for their antibacterial activity against K. pneumoniae, Shigella sp., M. luteus, E. coli and S. typhi. From this study, it was found that the activity of the ruthenium(III) Schiff base complexes almost reaches the effectiveness of the conventional bacteriocide standards. Copyright © 2009 John Wiley & Sons, Ltd.     

Hydrophosphination of boron–boron multiple bonds

Five compounds containing boron–boron multiple bonds are shown to undergo hydrophosphination reactions with diphenylphosphine in the absence of a catalyst. With diborenes, the products obtained are highly dependent on the substitution pattern at the boron atoms, with both 1,1- and 1,2-hydrophosphinations observed. With a symmetrical diboryne, 1,2-hydrophosphination yields a hydro(phosphino)diborene. The different mechanistic pathways for the hydrophosphination of diborenes are rationalised with the aid of density functional theory calculations.

Compounds containing boron–boron double and triple bonds are shown to undergo uncatalysed hydrophosphination reactions with diphenylphosphine.