Heterodimerization of olefins. 1. Hydrovinylation reactions of olefins that are amenable to asymmetric catalysis

Through a systematic examination of ligand and counterion effects, new protocols for a nearly quantitative and highly selective codimerization of ethylene and various functionalized vinylarenes have been discovered. In a typical reaction, 4-bromostyrene and ethylene undergo codimerization in the presence of 0.0035 equiv each of [(allyl)NiBr]2, triphenylphosphine, and AgOTf in CH2Cl2 at -56 degrees C to give 3-(4-bromophenyl)-1-butene in >98% yield and selectivity. Corresponding reactions with [(allyl)PdX]2 are much less efficient and less selective and may require further optimization before a viable system can be identified. Another useful protocol that gives comparable yield and selectivity involves the use of a single-component catalyst prepared from allyl 2-diphenylphosphinobenzoate, Ni(COD)2, and (C6F5)3B. Recognition of a synergistic relationship between a chiral hemilabile ligand (for example, (R)-2-methoxy-2'-diphenylphosphino-1,1'-binaphthyl, MOP) and a highly dissociated counteranion (BARF or SbF6) in an enantioselective version of the Ni-catalyzed reaction raises the prospects of developing a practical route for the synthesis of 3-arylbutenes. Several pharmaceutically relevant compounds, including widely used 2-arylpropionic acids, can be synthesized from these key intermediates. This reaction appears to be quite general. Synthesis of several new 2-diphenylphosphino-1,1-binaphthyl derivatives, prepared to probe the effect of hemilabile coordination on the efficiency and selectivity of the reaction, are also described.     

Effects of solvent on TEOS hydrolysis kinetics and silica particle size under basic conditions

In-situ liquid-state ²⁹Si nuclear magnetic resonance was used to investigate the temporal concentration changes during ammonia-catalyzed initial hydrolysis of tetraethyl orthosilicate in different solvents (methanol, ethanol, n-propanol, iso-propanol and n-butanol). Dynamic light scattering was employed to monitor simultaneous changes in the average diameter of silica particles and atomic force microscopy was used to image the particles within this time frame. Solvent effects on initial hydrolysis kinetics, size and polydispersity of silica particles were discussed in terms of polarity and hydrogen-bonding characteristics of the solvents. Initial hydrolysis rate and average particle size increased with molecular weight of the primary alcohols. In comparison, lower hydrolysis rate and larger particle size were obtained in the secondary alcohol. Exceptionally, reactions in methanol exhibited the highest hydrolysis rate and the smallest particle size. Ultimately, our investigation elaborated, and hence confirmed, the influences of chemical structure and nature of the solvent on the formation and growth of the silica particles under applied conditions.     

Organic–Inorganic Hybrid Supermicroporous Iron(III) Phosphonate Nanoparticles as an Efficient Catalyst for the Synthesis of Biofuels

Here we report a novel family of crystalline, supermicroporous iron(III) phosphonate nanomaterials (HFeP‐1‐3, HFeP‐1‐2, and HFeP‐1‐4) with different Fe^III‐to‐organophosphonate ligand mole ratios. The materials were synthesized by using a hydrothermal reaction between benzene‐1,3,5‐triphosphonic acid and iron(III) chloride under acidic conditions (pH≈4.0). Powder X‐ray diffraction, N₂ sorption, transmission and scanning electron microscopy (TEM and SEM) image analysis, thermogravimetric and differential thermal analysis (TGA‐DTA), and FTIR spectroscopic tools were used to characterize the materials. The triclinic crystal phase [P$\bar 1$ (2) space group] of the hybrid iron phosphonate was established by a Rietveld refinement of the PXRD analysis of HFeP‐1‐3 by using the MAUD program. The unit cell parameters are a=8.749(1), b=8.578(1), c=17.725(3) Å; α=104.47(3), β=97.64(1), γ=113.56(3)°; and V=1013.41 ų. With these crystal parameters, we proposed an 24‐membered‐ring open framework structure for HFeP‐1. Compound HFeP‐1‐3, with an starting Fe/ligand molar ratio of 3.0, shows the highest Brunauer–Emmett–Telller (BET) surface area of 556 m²g^?1 and uniform supermicropores of approximately 1.1 nm. The acidic surface of the porous iron(III) phosphonate nanoparticles was used in a highly efficient and recyclable catalytic transesterification reaction for the synthesis of biofuels under mild reaction conditions.     

New characterizations of digraphs represented by intervals

We present new characterizations of interval digraphs, interval graphs, and indifference digraphs, using linear orderings of edges and vertices. © 1996 John Wiley & Sons, Inc.     

On the robustness of least squares procedures in regression models

The criterion robustness of the standard likelihood ratio test (LRT) under the multivariate normal regression model and also the inference robustness of the same test under the univariate set up are established for certain nonnormal distributions of errors. Restricting attention to the normal distribution of errors in the context of univariate regression models, conditions on the design matrix are established under which the usual LRT of a linear hypothesis (under homoscedasticity of errors) remains valid if the errors have an intraclass covariance structure. The conditions hold in the case of some standard designs. The relevance of C. R. Rao's (1967 In Proceedings Fifth Berkeley Symposium on Math. Stat. and Prob., Vol. 1, pp. 355–372) and G. Zyskind's (1967, Ann. Math. Statist.38 1092–1110) conditions in this context is discussed.     

Conditional VaR estimation using Pearson’s type IV distribution

This paper presents a new value at risk (VaR) estimation model for equity returns time series and tests it extensively on Stock Indices of 14 countries. Two most important stylized facts of such series are volatility clustering, and non-normality as a result of fat tails of the return distribution. While volatility clustering has been extensively studied using the GARCH model and its various extensions, the phenomenon of non-normality has not been comprehensively explored, at least in the context of VaR estimation. A combination of extreme value theory (EVT) and GARCH has been explored to analyze financial data showing non-normal behavior. This paper proposes a combination of the Pearson’s Type IV distribution and the GARCH (1, 1) approach to furnish a new method with superior predictive abilities. The approach is back tested for the entire sample as well as for a holdout sample using rolling windows.     

Effect of time delay on a harvested predator-prey model

The predator-prey systems with harvesting have received a great deal of attentions for last few decades. Incorporating discrete time delays into predator-prey models could induce instability and bifurcation. In this paper we are interested in studying the combined effects of harvesting and discrete time delay on the dynamics of a predator-prey model. A comparative analysis is provided for stability behaviour in absence as well as in presence of time delay. The length of discrete time delay to preserve stability of the model system is obtained. Existence of Hopf-bifurcating small amplitude periodic solutions is derived by taking discrete time delay as a bifurcation parameter.     

Synthesis of Nanoporous Ni‐Co Mixed Oxides by Thermal Decomposition of Metal‐Cyanide Coordination Polymers

A straightforward strategy to prepare nanoporous metal oxides with well‐defined shapes is highly desirable. Through thermal treatment and a proper selection of metal‐cyanide coordination polymers, nanoporous nickel‐cobalt mixed oxides with different shapes (i.e., flakes and cubes) can be easily prepared. Our nanoporous materials demonstrate high electrocatalytic activity for oxygen evolution reaction.