Synthese von Nickelkomplexen mit porphinoidem Ligandsystem

Synthesis of nickel complexes with a porphine-type ligand system In the presence of nickel(II) salts the bicyclic vinylogous amidine 1 is dimerized to the diamagnetic (1-amino-10,20-diaza-octahydroporphinato)nickel(II) complex 3 . The condensation proceeds through a paramagnetic octahedral nickel(II) complex 2 . Starting from 3 , the (hexadecamethyl-10,20-diaza-hexahydroporphin)nickel bis (tetrafluoroborate) 7 (a (hexaaza [16]annulene)nickel(II) complex) was prepared in two steps. This highly electrophilic compound adds methoxide ions in consecutive and reversible steps to form first the (1-methoxy-10,20-diaza-octahydroporphinato)nickel tetrafluoroborate 8 and then the [cis-1, 11-dimethoxy-decahydroporphinato (2-)]nickel 6. 6, 7 and 8 were fully characterized and interconverted by addition and elimination reactions.     

INDO-Type calculations on the ground state and various ionic states of transition metal tricarbonyls

By means of the ΔSCF and transition operator (TO) methods based on a recently developed INDO extension to the first transition metal series, the first ionization potentials of benzene—chromium tricarbonyl ( I ), cyclopentadienyl manganese tricarbonyl ( II ), the iron—tricarbonyl complexes with trimethylenemethane ( III ), and cyclobutadiene ( IV ) have been calculated and compared with experimental data. It is shown that the electronic structure of I to IV can be rationalized by Hoffmann's fragment approach in both the ground state and the cationic hole states. Within the series I—IV there are remarkable energy differences in the ground state for MOs derived from the 1a₁ and 1e orbitals of the M(CO)₃ fragment. The observation that only one band is associated with the ionization events from MOs predominantly localized at the metal site is traced back to large relaxation effects. In the cationic hole states the split of the M(CO)₃ fragment orbitals 1a₁ and 1e is minute in all four compounds.     

Morphology and grafting of oxazoline-functional polymer particles with various carboxylic acids

Oxazoline-functionalized, crosslinked PMMA-particles, prepared by free radical nonaqueous dispersion polymerization, were grafted with n-decanoic acid and carboxylic acid-terminated polystyrene. Oxazoline groups, separated by an alkylspacer from the PMMA backbone, showed enhanced mobility with respect to the backbone, as evaluated by solid-state NMR spectroscopy using a dipolar filter. As a function of molecular mass of the carboxylic acid, the oxazoline conversion varied from 70 mol % for n-decanoic acid to 1% for monocarboxylate-terminated polystyrene CT-PS with M_n: 15,900 g/mol. Morphological studies, performed by TEM, showed that reaction with acid terminated polystyrene results exclusively in interfacial grafting at the particle surface. At low grafting levels a raspberry-like morphology was obtained, whereas grafting levels exceeding 14 wt % CT-PS resulted in core-shell morphology. Core-shell morphology was also verified by static light scattering using toluene solvent, which is isorefractive to the PMMA core. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1821–1827, 1998     

SPECTRAL ALBEDO MEASUREMENTS IN THE UV and VISIBLE REGION OVER DIFFERENT TYPES OF SURFACES

Abstract— The spectral albedo of the earth's surface, i.e. the ratio between spectral irradiance reflected by the ground to all directions and global irradiance, was measured by a spectroradiometer in the UV and visible region from 290 nm to 800 nm with a spectral resolution of 1.5 nm at steps of 2 nm in the UV (290–400 nm) and 10 nm in the visible (400–800 nm) region. The measurements were performed over bare fertile soil, sand at the beach, concrete (autobahn) and snow as well as over different types of vegetation (grass, oats, rye, sugar-beet, stubble). As the albedo increases with increasing wavelengths for most types of surfaces considered, it is smaller in the UV than in the visible region. In the UVB region (λ < 315 nm) the measured albedo is as small as 0.016-0.017 over vegetation, 0.04-0.05 over bare fertile soil, 0.07-0.10 over concrete ("autobahn") and 0.62-0.76% over polluted snow with a small wavelength dependence. A somewhat higher albedo occurs in the UVA region (315 < λ < 400 nm) with values ranging from 0.02 over vegetation to 0.05 to 0.08 over bare soil. The albedo over dry bright sand, which is typically found at the beach, is significantly higher (0.14 at 300 nm to 0.24 at 400 nm) than over other snow-free surfaces, thus leading to an enhanced dose of biologically effective radiation at the beach.     

1,3-dithiolanes from cycloadditions of alicyclic and aliphatic thiocarbonyl ylides with thiones: regioselectivity

The regiochemistry of 1,3-dithiolanes obtained from thiocarbonyl ylides 9 and thiones 10 shows a striking dependence on substituents. Previously and newly performed experiments indicate that sterically hindered cycloalkanethione S-methylides and dialkylthioketone S-methylides react with alicyclic and aliphatic thiones to give the 2,2,4,4-tetrasubstituted 1,3-dithiolanes 11 exclusively. Aryl groups in one or both reactants lead to a preference for, or even complete formation of, 4,4,5,5-tetrasubstituted 1,3-dithiolanes 12. Several mechanisms appear to be involved, but the paucity of experimental criteria is troubling. Quantum-chemical calculations (see preceding paper) on the cycloaddition between thioacetone S-methylide and thioacetone furnish lower activation energies for the concerted process than for the two-step pathways via C,S- or C,C-biradicals; the favoring of the 2,4-substituted 1,3-dithiolanes over the 4,5-substituted type would be expected to increase with growing bulk of substituents. Aryl groups stabilize intermediate biradicals. Experimental criteria for the differentiation of regioisomeric dithiolanes are discussed. Thiocarbonyl ylides 9 are prepared by 1,3-cycloadditions between diazomethane and thioketones and subsequent N(2) elimination from the usually isolable 2,5-dihydro-1,3,4-thiadiazoles 17; different ratios of the two rate constants lead to divergent product formation scenarios.     

Zur Synthese von Imidazo(2,1-b)-1,3,4-thiadiazolo(3,2-a)-pyrimidonen-(6)

2-Amino-6-aryl-imidazo(2,1-b)-1,3,4-thiadiazoles (1 a-f) were condensed with 1,3-ketocarboxylates e. g. ethyl-butyroacetate, ethyl-benzoylacetate, 4-nitrobenzoylacetate or ethyl-cyclopentanone(2)-carboxylate and ethyl-cyclohexanone(2)-carboxylate directly to imidazo(2,1-b)-1,3,4-thiadiazolo(3,2-a) pyrimidones-(6) (4 a-f, 5 a-f, 6 d, e, 7 a-f, 8 a, d).

11. Mitt. über Heterocyclen; 10. Mitt.Paul, H., Sitte, A., Wessel, R., Arch. Pharm. (Weinheim), im Druck.     

Comparative Studies of Different Quinolinone Derivatives as Donors in Fluorescence‐Resonance‐Energy Transfer (FRET) – Systems in Combination with a (Bathophenanthroline)ruthenium(II) Complex as Acceptor

We describe the preparation as well as a detailed photophysical study of Fmoc‐amino acid building blocks carrying different carbostyril (=quinolin‐2(1H)‐one) heterocycles as donors in a FRET (fluorescence‐resonance‐energy transfer) system in combination with a [Ru^II(bathophenanthroline)] complex (bathophenanthroline=4,7‐diphenyl‐1,10‐phenanthroline). The efforts resulted in a clear preference for building block 16 due to its ease of synthesis (Scheme 2), its chemical robustness, and the FRET efficiency when incorporated into peptides.     

Six-membered metalla-coronands. synthesis and crystal packing: columns, compartments, and 3D-networks

Reaction of various N-substituted diethanolamines H(2)L(3) (4) with calcium hydride and iron(III) chloride leads to the self-assembly of six-membered ferric wheels [Fe(6)X(6)(L(3))(6)] (5). Principally, all the iron coronands are isostructural; however, they differ fundamentally with respect to their crystal packing. Exemplarily, this is discussed for selected members of the space groups R, P, P2(1)/c, P2(1)/n, C2/c, and P. Depending on the nature of their sidearms, the ferric wheels create various substructures. For instance, the ferric wheels 5a-i of space group R or P are piled in parallel in cylindrical columns, which are surrounded by six parallel columns alternately dislocated by (1)/(3)c and (2)/(3)c against the central one. Pronounced van der Waals interactions give rise to compartmentation and incarceration of guest molecules as seen for 5e,g. However, in 5h strong pi-pi interactions create a three-dimensional scaffold. The most significant difference of the ferric wheels 5j-p of space groups P2(1)/c, P2(1)/n, and C2/c is that these ferric wheels are arranged in parallel in two orientations. They differ mainly only by the included angle of the two groups of parallel wheels. In the case of 5l, molecular chains are formed in the crystal due to pi-pi interactions. The ferric wheels 5q-y of space group P are packed in the crystal most simply, with all the ferric wheels piled in parallel.     

2,3‐Diaryl‐3‐hydroxy­propionic acid inter­mediates in the synthesis of threo forms of 1,2‐diaryl‐1,3‐propane­diols

Racemic threo‐3‐hydroxy‐2,3‐diphenyl­propionic acid, C₁₅H₁₄O₃, (I), crystallizes from ethyl acetate as a conglomerate of separate (+)‐ and (−)‐crystals. The geometries of (I) and its methyl ester are compared. Reduction of (I) gives threo‐1,2‐diphenyl‐1,3‐propane­diol. The synthesis of threo forms of 1,2‐diaryl‐1,3‐propane­diols via 2,3‐diaryl‐3‐hydroxy­propionic acids is discussed.     

Gemischt quantenmechanisch-statistische Modellrechnungen nach der Einzentrenmethode an Wasserstoffverbindungen tetraedrischer Symmetrie von Elementen der III., IV. und V. Hauptgruppe

Using a one-center-method, treating the inner shells statistically, the valence-shell, however, by quantum mechanics, the equilibrium internuclear distances and total molecular energies have been computed for CH₄, SiH₄, GeH₄, SnH₄, PbH₄, BH ₄ ^? , AlH ₄ ^? , GaH ₄ ^? , InH ₄ ^? , TlH ₄ ^? , NH ₄ ⁺ , PH ₄ ⁺ , AsH ₄ ⁺ , SbH ₄ ⁺ , and BiH ₄ ⁺ . The results are in good agreement with experimental data as well as with theoretical values.