Experimental and theoretical study of the complexation of the thallium cation with a hexaarylbenzene-based receptor

Abstract  

From extraction experiments in the two-phase water/nitrobenzene system and γ-activity measurements, the stability constant of a hexaarylbenzene-based receptor. Tl⁺ complex species dissolved in nitrobenzene saturated with water was determined. By using the quantum-mechanical density functional level of theory calculations, the most probable structure of this complex was derived.     

Mechanistic studies of ethylene hydrophenylation catalyzed by bipyridyl Pt(II) complexes

Cationic platinum(II) complexes [((t)bpy)Pt(Ph)(L)](+) [(t)bpy =4,4'-di-tert-butyl-2,2'-bipyridyl; L = THF, NC(5)F(5), or NCMe] catalyze the hydrophenylation of ethylene to generate ethylbenzene and isomers of diethylbenzene. Using ethylene as the limiting reagent, an 89% yield of alkyl arene products is achieved after 4 h at 120 °C. Catalyst efficiency for ethylene hydrophenylation is diminished only slightly under aerobic conditions. Mechanistic studies support a reaction pathway that involves ethylene coordination to Pt(II), insertion of ethylene into the Pt-phenyl bond, and subsequent metal-mediated benzene C-H activation. Studies of stoichiometric benzene (C(6)H(6) or C(6)D(6)) C-H/C-D activation by [((t)bpy)Pt(Ph-d(n))(THF)](+) (n = 0 or 5) indicate a k(H)/k(D) = 1.4(1), while comparative rates of ethylene hydrophenylation using C(6)H(6) and C(6)D(6) reveal k(H)/k(D) = 1.8(4) for the overall catalytic reaction. DFT calculations suggest that the transition state for benzene C-H activation is the highest energy species along the catalytic cycle. In CD(2)Cl(2), [((t)bpy)Pt(Ph)(THF)][BAr'(4)] [Ar' = 3,5-bis(trifluoromethyl)phenyl] reacts with ethylene to generate [((t)bpy)Pt(CH(2)CH(2)Ph)(η(2)-C(2)H(4))][BAr'(4)] with k(obs) = 1.05(4) × 10(-3) s(-1) (23 °C, [C(2)H(4)] = 0.10(1) M). In the catalytic hydrophenylation of ethylene, substantial amounts of diethylbenzenes are produced, and experimental studies suggest that the selectivity for the monoalkylated arene is diminished due to a second aromatic C-H activation competing with ethylbenzene dissociation.     

First order melting transitions of highly ordered dipalmitoyl phosphatidylcholine gel phase membranes in molecular dynamics simulations with atomistic detail

Molecular dynamics simulations with atomistic detail of the gel phase and melting transitions of dipalmitoyl phosphatidylcholine bilayers in water reveal the dependency of many thermodynamic and structural parameters on the initial system ordering. We quantitatively compare different methods to create a gel phase system and we observe that a very high ordering of the gel phase starting system is necessary to observe behavior which reproduces experimental data. We performed heating scans with speeds down to 0.5 K/ns and could observe sharp first order phase transitions. Also, we investigated the transition enthalpy as the natural intrinsic parameter of first order phase transitions, and obtained a quantitative match with experimental values. Furthermore, we performed systematic investigations of the statistical distribution and heating rate dependency of the microscopic phase transition temperature.     

Synergistic effects of encapsulated phthalocyanine complexes in MIL-101 for the selective aerobic oxidation of tetralin

Metal phthalocyanine complexes encapsulated in MIL-101, and used as "ship-in-a-bottle" catalysts, show outstanding TONs in the aerobic oxidation of tetralin.     

Asymptotic properties of sample quantiles of discrete distributions

The asymptotic distribution of sample quantiles in the classical definition is well-known to be normal for absolutely continuous distributions. However, this is no longer true for discrete distributions or samples with ties. We show that the definition of sample quantiles based on mid-distribution functions resolves this issue and provides a unified framework for asymptotic properties of sample quantiles from absolutely continuous and from discrete distributions. We demonstrate that the same asymptotic normal distribution result as for the classical sample quantiles holds at differentiable points, whereas a more general form arises for distributions whose cumulative distribution function has only one-sided differentiability. For discrete distributions with finite support, the same type of asymptotics holds and the sample quantiles based on mid-distribution functions either follow a normal or a two-piece normal distribution. We also calculate the exact distribution of these sample quantiles for the binomial and Poisson distributions. We illustrate the asymptotic results with simulations.     

Interpolating Thin-Shell and Sharp Large-Deviation Estimates for Lsotropic Log-Concave Measures

Given an isotropic random vector X with log-concave density in Euclidean space \mathbbRⁿ{\mathbb{R}^n} , we study the concentration properties of |X| on all scales, both above and below its expectation. We show in particular that

Line-by-line calculations of thermal infrared radiation representative for global condition: CFC-12 as an example

We estimate a current direct radiative forcing due to CFC-12 of 0.18 Wm^-2, which is likely to be the peak radiative forcing for CFC-12. Global measurements of CFC-12 show at present an almost negligible trend for CFC-12 and measurement in an industrialized region show evidence that the peak concentration is reached. It is expected that concentration of CFC-12 in industrialized regions begins to decline 1-3 years before the global concentration.Our radiative forcing calculations are based on a line-by-line model appropriate for simulation of global mean radiative forcing, including clouds and stratospheric temperature adjustment. The radiative forcing of 0.33 Wm^-2/ppbv is close to earlier published results for this compound. New spectroscopic measurements for CFC-12 are performed and compared to previously published results.