Beiträge zur Dispersoidchemie des Torfes. V

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Synthesis and structure of novel copper(II) complexes with pyrazole derived ligands and metal–ligand interaction in solution

Two new ligands of the coumarin type have been synthesized and characterized by ¹H, ¹³C NMR, IR and MS. The crystal and molecular structures of ligand 2, determined by the X-ray diffraction method, are presented. With copper(II) these ligands create solid complexes of the type CuLCl₂, where L is 5-(2-hydroxybenzoyl)-3-methyl-1-(2-pyridinyl)pyrazol-4-carboxylic acid methyl ester (2) or 3-methyl-1-(2-pyridinyl)-1H-chromene[4,3-c]pyrazol-4-on (3). The new copper(II) complexes have been characterized by elemental analysis and solid state FT-IR. The protonation constants of ligands 2 and 3 have been determined in 5% v/v 1,4-dioxane–water solution (25 °C). The coordination modes in the complexes with copper(II) are discussed for 2 on the basis of potentiometric and UV–Vis data.     

Note on the Stability of a Slowly Rotating Timoshenko Beam with Damping

This paper continues the senior author's previous investigation of the slowly rotating Timoshenko beam in a horizontal plane whose movement is controlled by the angular acceleration of the disk of the driving motor into which the beam is rigidly clamped. It was shown before that this system preserves the total energy. We consider the problem of stability of the system after introducing a particular type of damping. We show that the energy of only part of the system vanishes. We illustrate obtained solution with the critical case of the infinite value of the damping coefficient.     

Are linear algorithms always good for linear problems?

We exhibit linear problems for which every linear algorithm has infinite error, and show a (mildly) nonlinear algorithm with finite error. The error of this nonlinear algorithm can be arbitrarily small if appropriate information is used. We illustrate these examples by the inversion of a finite Laplace transform, a problem arising in remote sensing.     

Factor analysis of deuterium isotope effects on 13C NMR chemical shifts in Schiff bases

We have analyzed deuterium isotope effects on (13)C chemical shifts in a series of o-hydroxy Schiff bases by applying factor analysis. Two orthogonal factors were obtained that explain about 80 and 10 % of the variance of the data. The numerical values of these factors can be related to 1H NMR chemical shifts of the proton involved in the intramolecular bonds delta(XH) (X = O or N). Such a relation allows one to identify clusters of compounds with different tautomeric forms of hydrogen bonding. Application of a similar approach to solution 13C NMR chemical shifts produces three important factors, which have a different structure to factors describing isotope effects. This illustrates well the different nature of chemical shifts and isotope effects. The three factors explain about 54, 15, and 13 % of variance. They can be rationalized and are strongly related to the electronic properties and location of substituents.