I. Configurational stability and redistribution equilibria in organomagnesium compounds. II. Redistribution equilibria in organocadmium compounds

I. CONFIGURATIONAL STABILITY AND REDISTRIBUTION EQUILIBRIA IN ORGANOMAGNESIUM COMPOUNDS

The dependence of the rate of inversion of a dialkylmagnesium compound on the solvent has been studied.

Examination of the temperature dependence of the nuclear magnetic resonance spectrum of 1-phenyl-2-propylmagnesium bromide in diethyl ether solution indicates that inversion of configuration at the methylene group of this Grignard reagent occurs with an approximate rate of 2 sec^-1 at room temperature. This is the first example of a rapid inversion rate in a secondary Grignard reagent.

The rates of exchange of alkyl groups between dineopentylmagnesium and di-s-butylmagnesium, bis-(2-methylbutyl)-magnesium and bis-(4, 4-dimethyl-2-pentyl)-magnesium respectively in diethyl ether solution were found to be fast on the nmr time scale. However, the alkyl group exchange rate was found to be slow in a diethyl ether solution of dineopentylmagnesium and bis-(2-methylbutyl)-magnesium containing N, N, N', N'-tetramethylethylenediamine. The unsymmetrical species neopentyl-2-methylbutyl-magnesium was observed at room temperature in the nmr spectrum of the solution containing the diamine.

II. REDISTRIBUTION EQUILIBRIA IN ORGANOCADMIUM COMPOUNDS

The exchange of methyl groups in dimethylcadmium has been studied by nuclear magnetic resonance spectroscopy. Activation parameters for the methyl group exchange have been measured for a neat sample and for a solution in tetrahydrofuran. The exchange is faster in the basic solvent tetrahydrofuran relative to the neat sample and in tetrahydrofuran solution is retarded by the solvating agent N, N, N’, N’-tetramethylethylenediamine and greatly increased by cadmium bromide. The addition of methanol to a solution of dimethylcadmium in tetrahydrofuran appears to have very little effect on the rate of exchange. The exchange was found to proceed with retention of configuration. The rate-limiting step for the exchange of methyl groups in a basic solvent appears to be the dissociation of coordinating solvent from dimethylcadmium.

The equilibrium between methylcadmium bromide, dimethylcadmium and cadmium bromide in tetrahydrofuran solution has also been studied. At room temperature the interconversion of the species is very fast on the nmr time scale but at -100° distinct absorptions for methylcadmium bromide and imethylcadmium are observed.

The species ethylmethylcadmium has been observed in the nmr spectrum.

The rate of exchange of vinyl groups in a solution of divinylcadmium in tetrahydrofuran has been found to be fast on the nmr time scale.

Efficiency vs. Stability in a Mixed Network Formation Model

Documentos de Trabajo

Relativistic velocity - potential hydrodynamics and stellar stability

The equations of relativistic, perfect-fluid hydrodynamics are cast in Eulerian form using six scalar "velocity-potential" fields, each of which has an equation of evolution. These equations determine the motion of the fluid through the equation

U_ʋ=µ^-1 (ø,_ʋ + αβ,_ʋ + ƟS,_ʋ).

Einstein's equations and the velocity-potential hydrodynamical equations follow from a variational principle whose action is

I = (R + 16π p) (-g)^1/2 d⁴x,

where R is the scalar curvature of spacetime and p is the pressure of the fluid. These equations are also cast into Hamiltonian form, with Hamiltonian density –T₀⁰ (-g^oo)^-1/2.

The second variation of the action is used as the Lagrangian governing the evolution of small perturbations of differentially rotating stellar models. In Newtonian gravity this leads to linear dynamical stability criteria already known. In general relativity it leads to a new sufficient condition for the stability of such models against arbitrary perturbations.

By introducing three scalar fields defined by

ρ ᵴ = ∇λ + ∇x(xi + ∇xɣi)

(where ᵴ is the vector displacement of the perturbed fluid element, ρ is the mass-density, and i, is an arbitrary vector), the Newtonian stability criteria are greatly simplified for the purpose of practical applications. The relativistic stability criterion is not yet in a form that permits practical calculations, but ways to place it in such a form are discussed.

Stability analysis of RF amplifiers based on MIMO pole-zero identification

Spurious oscillations are one of the principal issues faced by microwave and RF circuit designers. The rigorous detection of instabilities or the characterization of measured spurious oscillations is still an ongoing challenge. This project aims to create a new stability analysis CAD program that tackles this chal- lenge. Multiple Input Multiple Output (MIMO) pole-zero identification analysis is introduced on the program as a way to create new methods to automate the stability analysis process and to help designers comprehend the obtained results and prevent incorrect interpretations. The MIMO nature of the analysis contributes to eliminate possible controllability and observability losses and helps differentiate mathematical and physical quasi-cancellations, products of overmodeling. The created program reads Single Input Single Output (SISO) or MIMO frequency response data, and determines the corresponding continuous transfer functions with Vector Fitting. Once the transfer function is calculated, the corresponding pole/zero diagram is mapped enabling the designers to analyze the stability of an amplifier. Three data processing methods are introduced, two of which consist of pole/zero elimina- tions and the latter one on determining the critical nodes of an amplifier. The first pole/zero elimination method is based on eliminating non resonant poles, whilst the second method eliminates the poles with small residue by assuming that their effect on the dynamics of a system is small or non-existent. The critical node detection is also based on the residues; the node at which the effect of a pole on the dynamics is highest is defined as the critical node. In order to evaluate and check the efficiency of the created program, it is compared via examples with another existing commercial stability analysis tool (STAN tool). In this report, the newly created tool is proved to be as rigorous as STAN for detecting instabilities. Additionally, it is determined that the MIMO analysis is a very profitable addition to stability analysis, since it helps to eliminate possible problems of loss of controllability, observability and overmodeling.

Reconciling yield stability with international fisheries agencies precautionary preferences: the role of non constant discount factors in age structured models

International fisheries agencies recommend exploitation paths that satisfy two features. First, for precautionary reasons exploitation paths should avoid high fishing mortality in those fisheries where the biomass is depleted to a degree that jeopardise the stock's capacity to produce the Maximum Sustainable Yield (MSY). Second, for economic and social reasons, captures should be as stable (smooth) as possible over time. In this article we show that a conflict between these two interests may occur when seeking for optimal exploitation paths using age structured bioeconomic approach. Our results show that this conflict be overtaken by using non constant discount factors that value future stocks considering their relative intertemporal scarcity.

Synthesis, spectroscopic properties and thermal stability of metal(II) tetraazaporphyrin complexes with two strong wavelength absorption

Three kinds of metal(II) tetraazaporphyrin complexes with blue-violet and red light wavelength absorption were synthesized by refluxing tetraazaporphyrin ligand and different metal(II) ions, respectively. Their structures were confirmed by elemental analysis, LDI-TOF-MS, FT-IR and UV-Vis. The solubility of metal(II) tetraazaporphyrin complexes in organic solvents and absorption properties of their chloroform solution and films on K9 glass in the region 250-800 nm were measured. The influence on the difference of absorption maximum from metal(II) tetraazaporphyrin complexes to tetraazaporphyrin ligand by different metal(II) ions was studied. In addition, the thermal stability of the complexes was also evaluated. (c) 2006 Elsevier Ltd. All rights reserved.

The intensity distribution and thermal stability of InnoSlab laser

Partially end-pumped slab laser is an innovative solid state laser, namely InnoSlab. Combining the hybrid resonator with partially end-pumping, the output power can be scaled with high beam quality. In this paper, the output intensity distributions are simulated by coordinate transformation fast Fourier transform (FFT) algorithm, comparing the thermal lens influence. As the simulated curves showed, the output mode is still good when the thermal lens effect is strong, indicating the good thermal stability of InnoSlab laser. Such a new kind of laser can be designed and optimized on the base of this simulation.

Thermal stability and spectroscopic properties of Er3+-doped niobium tellurite glasses for broadband amplifiers

Three Er3+-doped tellurite glasses with compositions of 70TeO(2)-30ZnO, 70TeO(2)-20ZnO-10Nb(2)O(5) and 70TeO(2)-20ZnO-5BaO-5Nb(2)O(5) have been investigated for developing fiber and planar broadband amplifiers and lasers. The optical spectroscopic properties and thermal stability of Er3+-doped tellurite glasses have been discussed. The results show that the incorporation of Nb2O5 increases the thermal stability of Er3+-doped tellurite glasses significantly, Er3+-doped niobium tellurite glasses 70TeO(2)-20ZnO-10Nb(2)O(5) and 70TeO(2)-20ZnO-5BaO-5Nb(2)O(5) exhibit the good thermal stability (DeltaT > 150degreesC), the large emission cross-section (>10 x 10(-21) cm(2)) and broad full width at half maximum (similar to65 nm), will be preferable for broadband Er3+-doped fiber amplifiers. (C) 2004 Elsevier B.V. All rights reserved.

Stability against crystallization and spectroscopic properties of Tm3+ doped fluorophosphate glasses

Fluorophosphate glasses with various content of Al(PO3)(3) were prepared. With the increment of Al(PO3)(3) content, density decreases while refractive index increases, and transition temperature, crystallization peak temperature and melt temperature increase which were suggested by differential scanning calorimetry. These glasses exhibit the best stability against crystallization with 7-9 mol'Yo Al(PO3)(3) content. Normalized Raman spectra were used to analyze structure and phonon state. The increment of Al(PO3)(3) content does not affect phonon energy but results in the augment of phonon density. Absorption spectra were measured. H-3(6) -> F-3(4) transition exhibits absorption at L band of the third communication window. Compared with the energy of Tm3+ excited states in other glass system, F-3(4) energy of Tm3+ in these glasses is considerable higher and H-3(4) energy is considerable lower, and it can be predicted that emission band of H-3(4) -> F-3(4) transition is close to the amplified band of gain-shift Tm3+ doped fiber amplifier. Analyses of Judd-Ofelt theory suggest when Al(PO3)(3) content is no more than 7 mol%, Judd-Ofelt parameters Omega(t) and the lifetime of H-3(4) energy level of TM3+ vary little with the increment of Al(PO3)(3) content, and when Al(PO3)(3) content is more than 7 mol%, Omega(2) and Omega(6) increase and radiative lifetime of H-3(4) energy level of Tm3+ drops sharply with the increment of Al(PO3)(3) content. (c) 2006 Elsevier B.V. All rights reserved.