Synthesis and characterization of Co(II) and Cu(II) supported complexes of 2-pyrazinecarboxylic acid for cyclohexene oxidation

The complexes [Co(N^O)₂] (1) and [Cu(N^O)₂] (2) {N^O = η²-(N,O) coordinated 2-pyrazinecarboxylic acid} have been synthesized and characterized by elemental (including metal) analyses, FT-IR spectroscopy and powder X-ray diffraction. The molecular structure of complex 2 was determined by single X-ray crystallography. In the molecule, the Cu atom occupies the center of a square planar geometry, which consists of two trans-O atoms and two trans-N atoms of two 2-pyrazinecarboxylic acid ligands. The complexes 1 and 2 were well encapsulated into zeolite–Y super-cage to yield the corresponding zeolite–Y encapsulated metal complexes, abbreviated herein as [Co(N^O)₂]–Y (3) and [Cu(N^O)₂]–Y (4). Similarly, the metal complexes 1 and 2 were immobilized on alumina and organically modified silica surfaces to lead to the formation of immobilized metal complexes [Co(N^O)₂]–Al₂O₃ (5); [Cu(N^O)₂]–Al₂O₃ (6); [Co(N^O)₂]–AMPS (7) and [Cu(N^O)₂]–AMPS (8) (AMPS = aminopropyl silica). Elemental (including metal) analyses, FT-IR spectroscopy, powder X-ray diffraction and thermal analysis have been used to characterize these materials. The catalytic activity of all the catalysts 1–8 towards the oxidation of cyclohexene into different chemically and pharmaceutically important products were evaluated under homogeneous and heterogeneous conditions. In order to obtain a maximum conversion of cyclohexene, the reaction parameters, like reaction temperature and time, were optimized. Under the optimized conditions, a maximum of 90.47% cyclohexene conversion was achieved with [Cu(N^O)₂]–Y (4) with a 1:2 molar ratio reaction of cyclohexene and H₂O₂.     

A Rare Phenoxido/Acetato/Azido Bridged Trinuclear and an Unprecedented Phenoxido/Azido Bridged One-Dimensional Polynuclear Nickel(II) Complexes: Synthesis, Crystal Structure, and Magnetic Properties with Theoretical Investigations on the Exchange Mechanism

The reaction of a tridentate Schiff base ligand HL (2-[(3-dimethylaminopropylimino)-methyl]-phenol) with Ni(II) acetate or perchlorate salts in the presence of azide as coligand has led to two new Ni(II) complexes of formulas [Ni(3)L(2)(OAc)(2)(μ(1,1)-N(3))(2)(H(2)O)(2)]·2H(2)O (1) and [Ni(2)L(2)(μ(1,1)-N(3))(μ(1,3)-N(3))](n)(2). Single crystal X-ray structures show that complex 1 is a linear trinuclear Ni(II) compound containing a μ(2)-phenoxido, an end-on (EO) azido and a syn-syn acetato bridge between the terminal and the central Ni(II) ions. Complex 2 can be viewed as a one-dimensional (1D) chain in which the triply bridged (di-μ(2)-phenoxido and EO azido) dimeric Ni(2) units are linked to each other in a zigzag pattern by a single end-to-end (EE) azido bridge. Variable-temperature magnetic susceptibility studies indicate the presence of moderate ferromagnetic exchange coupling in complex 1 with J value of 16.51(6) cm(-1). The magnetic behavior of 2 can be fitted in an alternating ferro- and antiferromagnetic model [J(FM) = +34.2(2.8) cm(-1) and J(AF) = -21.6(1.1) cm(-1)] corresponding to the triple bridged dinuclear core and EE azido bridge respectively. Density functional theory (DFT) calculations were performed to corroborate the magnetic results of 1 and 2. The contributions of the different bridges toward magnetic interactions in both compounds have also been calculated.     

Photoinitiated polymerization of styrene from self‐assembled monolayers on gold. II. Grafting rates and extraction

Ultrathin films of polystyrene (PS) were grown from self‐assembled monolayers by the “grafting‐from” technique. The initiating system consisted of a dithiol azobisisobutyronitrile‐type free‐radical initiator that was activated by irradiation at 300 nm. The thickness of the PS films ranged from 7 to 190 nm and could be controlled by varying the reaction time or the monomer concentration. The films were characterized by ellipsometry and Fourier transform‐reflection absorption infrared spectroscopy after Soxhlet extraction of residual physisorbed polymer. These films were unstable above 60 °C, and a water‐jacketed Soxhlet extractor was designed to maintain solvent temperatures below 45 °C during extraction. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3284–3291, 2002     

Electrostatic sheath at the boundary of a collisional dusty plasma

Considering the Boltzmann response of the ions and electrons in plasma dynamics and inertial dynamics of the dust charged grains in a highly collisional dusty plasma, the nature of the electrostatic potential near a boundary is investigated. Based on the fluid approximation, the formation as well as the characteristic behaviours of the sheath is studied. It is expected that the presence of dust charged grains will lead to a very different behaviour of the sheath as compared to that of electron-ion plasma. Moreover, the collisions of the dust charged grains with the neutrals are expected to exhibit novel features.     

Time series of functional data with application to yield curves

We develop time series analysis of functional data observed discretely, treating the whole curve as a random realization from a distribution on functions that evolve over time. The method consists of principal components analysis of functional data and subsequently modeling the principal component scores as vector autoregressive moving averag (VARMA) process. We justify the method by showing that an underlying ARMAH structure of the curves leads to a VARMA structure on the principal component scores. We derive asymptotic properties of the estimators, fits, and forecast. For term structures of interest rates, these provide a unified framework for studying the time and maturity components of interest rates under one setup with few parametric assumptions. We apply the method to the yield curves of USA and India. We compare our forecasts to the parametric model that is based on Nelson‐Siegel curves. In another application, we study the dependence of long term interest rate on the short term interest rate using functional regression.