Structure of enantiopure and racemic alanine adlayers on Cu(1 1 0)

Plane wave density functional theory has been employed to analyze the structure of alanine adlayers on the Cu(1 1 0) surface. Alanine forms (3 × 2) adlayers on Cu(1 1 0) that are closely related to the structures of glycine on the same surface. There is essentially no energy difference between the most stable racemic and enantiopure alanine adlayers. This observation implies that adsorption of racemic alanine on Cu(1 1 0) will result in a pseudoracemate adlayer.     

Synthesis, decomposition, and structural studies in the gas phase and solid state of N,N-dimethylaminoxygermane

N,N-Dimethylaminoxygermane, H3GeONMe2, was prepared by the reaction of H3GeBr with LiONMe2 in dimethyl ether at -96 degrees C. The identity of H3GeONMe2 was proven by gas-phase IR and solution NMR spectroscopy (1H, 13C, 15N, 17O). It is an unstable volatile liquid compound. It decomposes by cleavage of a Ge-O and a Ge-H bond giving HONMe2 and an insoluble germanium hydride polymer (GeH2)n. This decomposition reaction has been modeled at the MP2/6-311G(d,p) level of theory by the homodesmotic reaction H3GeONMe2 + Ge2H6-->Ge3H8 + HONMe2, which is predicted slightly exothermic by 14 kJ mol-1. The molecular structure of H3GeONMe2 was determined by gas-phase electron diffraction supported by an ab initio geometry [MP2/6-311G(d,p)] and a force field [MP2/6-31G(d)]. The structure of the compound in the crystal lattice was determined by low-temperature crystallography using a single crystal of H3GeONMe2 grown in situ [C2H9NOGe, orthorhombic, Pnma, Z = 4, a = 8.1280(12) A, b = 9.7037(15) A, c = 7.0722(12) A]. Important bond lengths and angles (gas phase/solid state, A/deg) are Ge-O 1.785(2)/1.815(1), O-N 1.462(7)/1.460(2), N-C 1.460(4)/1.453(2), Ge-O-N 105.2(5)/104.6(1), O-N-C 105.8(5)/105.8(1), C-N-C 110.8(9)/111.2(2), Ge...N 2.587(6)/2.601(1). In the solid state the compound forms infinite chains by intermolecular Ge...O contacts of 2.808 A. The question of the attraction between Ge and N atoms is discussed with respect to reference Ge/O and N/O compounds, which have wider angles at oxygen than H3GeONMe2. For comparison the structures of the compounds H3CONMe2, H3SiONMe2, and H3SnONMe2 were also calculated to reflect the influence of the group 14 atom on the structure and to discuss the occurrence of weak E...N interactions in the compounds H3EONMe2.     

Dynamic interaction of theory and experiment: total determination of the gas-phase molecular structure of tri-tert-butylphosphine oxide (OPBut3)

A new method to aid the determination of structures of sterically crowded molecules in the gas phase by dynamically linking the gas-phase electron diffraction (GED) refinement process with computational methods has been developed. The procedure involves refining the heavy-atom skeleton of the molecule using the GED data while continually updating the light-atom positions during the refinement using computational methods, in this case molecular mechanics. This removes errors associated with the assumption of local symmetry for the light-atom groups, which can affect the final values of the heavy-atom parameters. The refinement of the molecular structure of tri-tert-butyl phosphine oxide has been used to illustrate this new technique, which we call the DYNAMITE (DYNAMic Interaction of Theory and Experiment) method. Re-examination of the structure using this method has resulted in a shorter P-O distance than was found in a less sophisticated anaylsis, and is consistent with the molecule being regarded as O=PBut3, rather than O(-)-P+But3.     

Multifunctional redox catalysts as selective enhancers of oxidative stress

Certain cancer cells proliferate under conditions of oxidative stress (OS) and might therefore be selectively targeted by redox catalysts. Among these catalysts, compounds containing a chalcogen and a quinone redox centre are particularly well suited to respond to the presence of OS. These catalysts combine the specific electrochemical features of quinones and chalcogens. They exhibit high selectivity and efficiency against oxidatively stressed rat PC12, human Jurkat and human Daudi cells in cell culture, where their mode of action most likely involves the catalytic activation of existent and the generation of new reactive oxygen species. The high efficiency and selectivity shown by these catalysts makes them interesting for the development of anti-cancer drugs.     

Synthesis and derivatization of ethynyl alpha,alpha-dibromomethyl ketones: formation of highly functionalized vinyl triflates

[reaction: see text] We describe the synthesis of alpha,alpha-dibromomethyl ynones (8) and their subsequent derivatization to vinyl acetates (10). These vinyl acetates feature a 1,1-dibromo-olefin moiety, which is readily exploited in palladium-catalyzed Sonogashira, Stille, and Suzuki cross-coupling reactions with alkynes, stannanes, and boronic acids, respectively. A novel one-pot process then directly converts the resulting vinyl acetates 11-13 to the vinyl triflate derivatives 14a-j.     

Synthesis of monofluorinated 1-(naphthalen-1-yl)piperazines

A series of regioisomerically monofluorinated 1-(naphthalen-1-yl)piperazines is described.