Complexes with a Pincers. 2,6-Diphenylpyridine as Twofold-Deprotonated (C ∧ N ∧ C) terdentate ligand in C,C-trans-, and as mono-deprotonated (C ∧ N) chelate ligand in chiral C,C-cis-complexes of platinum(II) and palladium(II). Preliminary communication

2,6-Diphenylpyridine forms, as twofold-deprotonated, terdentate ligand, complexes with Pt(II) and Pd(II), having two adjacent five-membered metallocycles. As mono-deprotonated, bidentate ligand, it forms cis-bis-complexes having a chirality axis. Pt(II) complexes undergo thermal and photochemical oxidative addition reactions, yielding stable Pt(IV) compounds. Pd(II) complexes yield substitued 2,6-diphenylpyridine in photochemical reactions.     

Transient processes in photogalvanic cells: Part I. Fundamentals

The theory of transient processes in photogalvanic cells is developed. The systems treated consist of a photoactive species B which can be oxidized (or reduced) to A in its excited state B^* by a one-electron acceptor Z which itzelf is reduced (oxidized) to Y. It is further assumed that both redox couples undergo one-electron transfer reactions at the metal electrodes. The electrode kinetics for both redox couples is taken into account. A computer program is described with which the following data can all be obtained as functions of time, after illumination has started: current, potential of the illuminated electrode, potential of the dark electrode, power, and the concentration profiles of A, B, Z and Y near the electrodes.     

Some mechanisms for subtle influences of stereochemical composition on the physical properties of macromolecules

Coarse‐grained chains can be designed so that they successfully capture subtle effects arising from the local covalent structure of real chains. Constraining the conformations of the coarse‐grained chains with an appropriate rotational isomeric state model can achieve this objective. This claim has been documented by simulations of the dependence of the mixing behavior of polypropylene melts on the stereochemical composition of the chains; atactic polypropylene and isotactic polypropylene are miscible, but the replacement of either component with syndiotactic polypropylene can lead to immiscibility. This has also been documented by a comparison of simulations and infrared–visible sum frequency generation spectroscopy studies of the surface structures of atactic polystyrene and random copolymers of ethylene and propylene. The success of this method when the stereochemical composition is defined by side chains as small as CH₃ suggests that it should also be applicable to other problems in which the influence of the stereochemical composition is less subtle because the stereochemistry is defined by larger side chains. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1271‐1282, 2005     

O deficiency in the rutile TiO2 (110) surface: Ab initio quantum chemical investigation of the electronic properties

The (110) surface of rutile TiO₂ (110) has been modeled using a density functional theory (DFT) plane‐wave pseudo‐potential method (CASTEP). In this study, 6 and 9 atomic‐layer slabs have been examined. The stoichiometric surface converges to a low‐spin solution in both cases with a density of states (DOS) similar to that for the bulk. O deficiencies are introduced by the removal of neutral O atoms thus leaving a neutral model with a surfeit of 2 e^? per vacancy. This results in the partial filling of the Ti t_2g conduction band orbitals and a compensatory shift in the Fermi level. The reduced surface converges to a high‐spin solution in all cases, with the excess spin located within the previously unoccupied Ti t_2g orbitals. Removal of the bridging surface O atoms results in an excess spin of 2 electrons per unit cell with approximately one‐half that for removal of in‐plane surface O atoms and subsurface O atoms. The removal of O atoms from the surface leads to an increase of the band gap, with the largest increase due to the removal of in‐plane 3‐fold coordinated surface O atoms, and the smallest one due to the removal of subsurface O atoms. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Complexes of Rhodium(III) with Two Chelating C⁁N Ligands and One Diimine Ligand

The synthesis of two series of cyclometalated Rh^III compounds is described, namely of 5 dinuclear chlorobridged species [{Rh(C?N)₂} (μ-Cl)₂] A and of 15 mononuclear complexes [Rh(C?N)₂(N?N)]⁺ B ; C?N stands for five different cyclometalating ligands, i.e. deprotonated phenylpyridine, deprotonated 2-(thienyl)pyridine, and three deprotonated 1-aryl-1H-pyrazoles, and N?N for six diimine ligands such as 2,2-bihyridine, 2,2′-bi-1H-imidazole, and 2,2′-bipyrimidine. For (2,2′-bipyridine)bis[2-(thien-2-yl)pyridinato-N,C^3′]rhodium(III) chloride, an X-ray structure determination was carried out. In the other cases, ¹H-NMR spectra established the configuration of the complexes. All mononuclear and dinuclear complexes show a C,C cis-configuration. The UV/VIS-absorption bands at longest wavelength are most likely due to metal-to-ligand charge-transfer (MLCT) transitions, depending on the nature of the cyclometalating ligand C?N and on the diimine ligand N?N. The receptor orbital is in some cases on the cyclometalating ligand, in others on the diimine. All monomer complexes exhibit at least one reversible reduction wave in the cyclovoltammogram in dimethylformamide solutions, attributable to a ligand-centered reduction. It is, therefore, concluded that the LUMO in [Rh(C?N)₂(N?N)]⁺ is of L(π*) character, as opposed to [Rh(bpy)₃]³⁺, where it is a metal d-orbital. The crystal system of (2,2′-bipyridine)bis[2-(thien-2-yl)pyridinato-N,C_3′]rhodium(III) chloride—water (1/2.125) is tetragonal (space group P⁴; R = 0.036, R_w = 0.040). The Rh-atom has slightly distorted octahedral environment; the average distances are (Rh? N/thienyl? pyridine) = 2.060 (3), Rh? C = 1.9885 (3), and Rh? N(bipyridine) = 2.1415 (3) Å. Of the three ligands the 2,2′-bipyridine is the most planar.     

Podophyllum- Lignane: Struktur und Absolutkonfiguration von Podorhizol-β-D-glucosid ( = Lignan F). 19. Mitt. über mitosehemmende Naturstoffe [1]

Podorhizol-β-D -glucoside ( 1 ) ( = lignan F), C₂₈H₃₄O₁₃, a new lignan from the roots and rhizomes of Podophyllum species, represents one of the rare glucosides which are cleaved by acids as well as by bases. Acid hydrolysis furnished the intact aglycone podorhizol ( 3 ) and in addition two cyclisation products characterized as desoxy-podophyllotoxin ( 10 ) and (?)-isodesoxypodophyllotoxin ( 11 ), respectively. Base catalysed fission of the glucoside 1 yielded D -glucose and anhydropodorhizol ( 9 ). Podorhizol was smoothly oxidized to the corresponding ketone podorhizone ( 5 ), which upon treatment with NaOCH₃ underwent cleavage into methyl 3,4,5-trimethoxy-benzoate ( 8 ) and the benzylbutyrolactone derivative 7 . These findings combined with spectroscopical evidence revealed the structure of podorhizol as a 2,3-dibenzylbutyrolactone derivative.     

Zur Kenntnis von Ba(MgZn)V2O8, BaMn2V2O8 und Ba1/2Sr1/2Ni2V2O8

On Ba(MgZn)V₂O₈, BaMn₂V₂O₈, and Ba_1/2Sr_1/2Ni₂V₂O₈ Ba(Mg, Zn)V₂O₈ (A), BaMn₂V₂O₈ (B) and Ba_1/2Sr_1/2Ni₂V₂O₈ (C) were prepared by solid state reactions (A and B) and crystallization from a melt (C) respectively. (A? C) crystallize in the space group: D-I4₁/acd, Nr. 142. [Lattice constants (A): a = 12.4524(57) Å, c = 8.4408(36) Å; (B): a = 12.5563(14) Å, c = 8.5942(9) Å; (C): a = 12.2248(20) Å, c = 8.3245(15) Å]. (A), (B) and (C) are isotypic to SrNi₂V₂O₈ but showing higher symmetry.     

A proper account of core-polarization with pseudopotentials: single valence-electron alkali compounds

A polarization potential is incorporated into semi-empirical and Hartree-Fock adjusted pseudopotentials. For molecules, the pseudopotentials become geometry-dependent. The omission of this effect has been the reason for too smallR_e values in earlier semi-empirical work. Very accurate results are obtained for the dimer and hydride ions of alkali elements up to K.     

The synthesis of pyridine derivatives from 3-formylchromone

3-Formylchromone ( 1 ) reacts with active methylene derivatives to yield condensation products 2a-d, 10,11 and 12 . Treatment of 2a-d with ammonia or methylamine gives pyridines 3–6 . Alternatively, reaction of 1 with enamine derivatives yields pyrido compounds 15, 17, 19, 21, 23 and 28 in one step. Factors determining the formation and regiospecificity of the pyridine ring forming reactions are also discussed.     

Fragmentation studies of noncovalent sugar-sugar complexes by infrared atmospheric pressure MALDI

An investigation of sugar-sugar noncovalent complex fragmentation was conducted using a 2.94 microm Er:YAG laser for infrared (IR) atmospheric pressure matrix-assisted laser desorption/ionization (AP MALDI) on an ion trap mass spectrometer (ITMS). This approach allowed the analysis of weak noncovalent complexes between a variety of biologically relevant oligosaccharides. The strength of interaction varied with different sugar structures, potentially due to varying strength of hydrogen bonding networks. In some cases, fragmentation of intramolecular sugar bonds preceded breakdown of the noncovalent complex. This result appeared primarily when complexes contained sugars with at least one sialic acid. Globotrios dimers also showed intramolecular fragmentation in preference to breakdown of the noncovalent dimer. This technique will allow further study of sugar-sugar interactions known to play a role in cellular interactions.