Kondensationen von Chlorkohlensäure-cholsäureäthylester mit Aminen und Phenolen

Ohne Zusammenfassung     

Complete characterization of almost Moore digraphs of degree three

It is well known that Moore digraphs do not exist except for trivial cases (degree 1 or diameter 1), but there are digraphs of diameter two and arbitrary degree which miss the Moore bound by one. No examples of such digraphs of diameter at least three are known, although several necessary conditions for their existence have been obtained. In this paper, we prove that digraphs of degree three and diameter k ≥ 3 which miss the Moore bound by one do not exist. © 2004 Wiley Periodicals, Inc. J Graph Theory 48: 112–126, 2005     

Kinetics of the reactions of the hydroxyl radical with dimethyl ether and diethyl ether

Absolute rate coefficients for the reactions of the hydroxyl radical with dimethyl ether (k₁) and diethyl ether (k₂) were measured over the temperature range 295–442 K. The rate coefficient data, in the units cm³ molecule^?1 s^?1, were fitted to the Arrhenius equations k₁ (T) = (1.04 ± 0.10) × 10^?11 exp[?(739 ± 67 cal mol^?1)/RT] and k₂(T) = (9.13 ± 0.35) × 10^?12 exp[+(228 ± 27 kcal mol^?1)/RT], respectively, in which the stated error limits are 2σ values. Our results are compared with those of previous studies of hydrogen-atom abstraction from saturated hydrocarbons by OH. Correlations between measured reaction-rate coefficients and C? H bond-dissociation energies are discussed.     

Supramolecular dimer formation through hydrogen bond extensions of carboxylate ligands – Path for magnetic exchange

A new complex of unusual composition [Cu(3-O₂Nbz)₂(nia)(H₂O)₂] (1) (nia = nicotinamide, 3-O₂Nbz = 3-nitrobenzoate) has been prepared and studied together with two other complexes of composition [Cu(4-O₂Nbz)₂(nia)₂(H₂O)₂] (2) and [Cu(4-O₂Nbz)₂(nia)₂]?(4-O₂NbzH)₂ (3) (4-O₂Nbz = 4-nitrobenzoate). The composition of all complexes has been determined by elemental analysis, the complexes have been studied by electronic, infrared and EPR spectroscopy, as well as by magnetization measurements over the temperature range 1.8–300 K, and their structures have been solved. The structure of complex (1) consists of molecules, where Cu(II) atom is monodentately coordinated by the pair of 3-nitrobenzoato anions in trans  -positions together with water and nicotinamide molecules, forming nearly tetragonal basal plane, and by another water molecule in axial position of tetragonal-pyramidal coordination polyhedron. The neighboring molecule coordination polyhedron basal planes are coplanar and allow formation of supramolecular dimers with strong H-bonds between hydrogen atoms from equatorially coordinated water molecules and uncoordinated carboxylate oxygen atoms thus giving the nearest Cu?$?$Cu distance of 4.886(2) Å. Magnetization measurements showed that complex (1) exhibits maximum of magnetic susceptibility at 6.5 K and a fit to Bleaney-Bowers equation gave singlet–triplet energy gap 2J = −6.25 cm⁻¹, and zJ′ = −0.03 cm⁻¹. This might be an experimental proof that the carboxylate bridges extended with hydrogen bonds are the pathway of the spin–spin interactions. The temperature dependence of changes in EPR spectra of (1) and the spectrum at 4.2 K have confirmed its hydrogen bonded dimeric structure. The calculated Cu?$?$Cu distance 4.8 Å is in very good agreement with the value obtained from crystal structure. The complexes (2) and (3) at 300 K exhibit magnetic moment μ_eff = 1.98 B.M. and μ_eff = 1.84 B.M., respectively. These values practically do not change with lowering the temperature up to 5 K and only small drops to μ_eff = 1.87 B.M. (for (2)) and μ_eff = 1.79 B.M. (for (3)) at 1.8 K have been observed. The EPR spectra of complex (2) at room temperature as well as at 77 K are of axial type with g_⊥ = 2.062 and g_|| = 2.285 and exhibit resolved parallel hyperfine splitting with A_|| = 160 Gauss. The EPR spectra of complex (3) at room temperature as well as at 77 K are of axial type with g_⊥ = 2.065 and g_|| = 2.235 and exhibit unresolved parallel hyperfine splitting. EPR spectra of (2) and (3) are consistent with the X-ray structure.