Preparation, characterization, and condensation of copper tellurolate clusters in the pores of periodic mesoporous silica MCM-41

The copper-tellurolate cluster [(Cu(6)(TePh)(6)(PPh(2)Et)(5)] has been loaded into the pores of MCM-41 by solid-state impregnation techniques. It was found that the best loading conditions are 110 degrees C and 10(-)(3) Torr static vacuum. The resulting material was analyzed by powder X-ray diffraction (PXRD), nitrogen adsorption isotherms, thermogravimetric analysis (TGA), (31)P CP MAS NMR spectroscopy, and TEM. It was observed that loading is accompanied by loss of the phosphine shell, with retention of the copper-tellurium core. Condensation of the impregnated material may proceed thermally or photochemically. Thermal condensation results in the formation of Cu(2)Te nanoparticles as demonstrated by PXRD, and TEM data suggests that the process has taken place inside the pores of MCM-41. Photochemical condensation yields larger metal-chalcogen clusters in the pores as suggested by the result of UV-vis diffuse reflectance spectroscopy and TEM measurements.     

Synthesis and Reaction of the First 1,2‐Oxaphosphetane Complexes

While P^V 1,2‐oxaphosphetanes are well known from the Wittig reaction, their P^III analogues are still unexplored. Herein, the synthesis and reactions of the first 1,2‐oxaphosphetane complexes are presented, which were achieved by reaction of the phosphinidenoid complex [Li(12‐crown‐4)(solv)][(OC)₅W{(Me₃Si)₂HCPCl}] with different epoxides. The title compounds appeared to be stable in toluene up to 100 °C, before unselective decomposition started. Acid‐induced ring expansion with benzonitrile resulted in selective formation of the first complex bearing a 1,3,4‐oxazaphosphacyclohex‐2‐ene ligand.     

Density functional theory study of water adsorption on FeOOH surfaces

Using density functional theory (DFT) calculations with an on-site Coulomb repulsion term, we study the composition, stability, and electronic properties of the most common FeOOH surfaces goethite(101), akaganeite(100), and lepidocrocite(010), and their interaction with water. Despite the differences in surface structure, the trends in surface stability of these FeOOH polymorphs exhibit remarkable similarities. We find that the reactivity and the binding configuration of adsorbates depend strongly on the coordination of surface iron: at the fourfold coordinated Fe2 site water is chemisorbed, whereas at the fivefold coordinated Fe1 water is only loosely bound with hydrogen pointing towards the surface. Our results show that the oxidation state of surface iron can be controlled by the surface termination where ferryl (Fe^4 +) species emerge for oxygen terminated surfaces and ferrous iron (Fe^2 +) at iron and water terminations leading to a reduced band gap. In contrast, the fully hydroxylated surfaces, identified as stable surface configurations at standard conditions from the surface phase diagram, show electronic properties and band gaps closest to bulk FeOOH with ferric surface iron (Fe^3 +). Only in the case of goethite(101), a termination with mixed surface hydroxyl and aquo groups is stabilized.     

Direct contact versus solvent-shared ion pairs in NiCl2 electrolytes monitored by multiplet effects at Ni(II) L edge X-ray absorption

We investigate the local electronic structure in aqueous NiCl2 electrolytes by Ni L edge X-ray absorption spectroscopy. The experimental findings are interpreted in conjunction with multiplet calculations of the electronic structure and the resulting spectral shape. In contrast to the situation in the solid, the electronic structure in the electrolyte reflects the absence of direct contact Ni-Cl ion pairs. We observe a systematic change of the intensity ratio of singlet- and triplet-related spectral features as a function of electrolyte concentration. These changes can be described theoretically by a change in the weight of transition matrix contributions with different symmetries. We interpret these findings as being due to progressive distortions of the local symmetry induced by solvent-shared ion pairs.     

Direct organocatalytic aldol reactions in buffered aqueous media

Organocatalytic cross-aldol reactions catalyzed by cyclic secondary amines in aqueous media provide a direct route to a variety of aldols including carbohydrate derivatives and may warrant consideration as a prebiotic route to sugars.     

13C- and 1H-NMR. Spectra of ortho-benzoquinones. On the assignment problem in 13C spectra

¹³C- and ¹H-NMR. spectra of ortho-benzoquinone 1 and its methyl derivatives have been analysed. By means of heteronuclear double resonance experiments it is shown that assignments given in the literature for the olefinic carbon resonances of 1 and of a series of substituted ortho-benzoquinones have to be inverted. ¹³C-carbonyl frequencies of various six-membered cyclic ketones are presented.     

Speckle imaging of spin fluctuations in a strongly interacting Fermi gas

Spin fluctuations and density fluctuations are studied for a two-component gas of strongly interacting fermions along the Bose-Einstein condensate-BCS crossover. This is done by in?situ imaging of dispersive speckle patterns. Compressibility and magnetic susceptibility are determined from the measured fluctuations. This new sensitive method easily resolves a tenfold suppression of spin fluctuations below shot noise due to pairing, and can be applied to novel magnetic phases in optical lattices.     

Tris(thioacetals) from benzene hexathiol: towards covalent self-assembly

Mixtures of isomers are available from the reaction of benzene hexathiol with three equivalents of p-tolualdehyde and kinetic traps avoided under the reported catalytic conditions, establishing tris(thioacetals) as potential building blocks for covalently self-assembled complex structures.