Copper(II)–Ammonia Complexation Equilibria in Aqueous Solutions at Temperatures from 30 to 250°C by Visible Spectroscopy

The spectra of copper(II)–ammonia solutions in 2 mol-kg^–1 NH₄NO₃(aq) were recorded as a function of pH with a new UV–visible flow cell, capable of operating at conditions up to 325°C and 300 bars. Equilibrium constants for the formation of copper(II)–ammonia complexes Cu(NH₃)_n ²⁺, 1 n 4, from 30 to 150°C were determined by evolving factor analysis and nonlinear least-squares regression. Measurements at higher temperatures were limited by thermal decomposition of NH₄NO₃(aq). The formation constants of Cu(NH₃)_n ²⁺ decrease with temperature, consistent with extrapolations of literature data from measurements below 100°C. Measurements above 150°C were carried out in 0.5 mol-kg^–1 CF₃SO₃H (aq), at the very high ammonia concentrations required to avoid the precipitation of CuO(s). The spectra are consistent with Cu(NH₃)₄ ²⁺ as the predominant species, based on extrapolations of peak maxima and molar absorptivities from lower temperatures. Shifts in the spectra of Cu²⁺ and the Cu(NH₃)_n ²⁺ species to higher wavelength and increases in molar absorbance with increasing temperature are discussed in terms of the structure of the complexes.     

Studies on the Reactivity of 4-Acetoxy-3-acylamino-2-azetidinones: Stereospecific trans Carbon-Carbon Bond Formation

The recent publication of Reuschling and co-workers2 on the synthesis of a carbapenem utilizing, as the key step in the sequence, the stereospecific C-C coupling of 3-substituted-acetoxy-2-azetidinones with cuprates, prompts us to report our related work in this area.     

On the photoelectron spectrum of sulphur trioxide

He(I), He(II) and variable temperature Ne(I) photoelectron spectra of sulphur trioxide are reported. All six of the expected ionic states have been detected and assigned; the assignment differs from a previous one. Ab initio calculations in a medium basis set have been carried out and spectral intensities have been calculated; agreement between the calculations and the spectra is good. The calculations show a substantial S(3d) character in the S-O bond, and the spectra are consistent with this.     

Design of electromagnetic cloaks and concentrators using form-invariant coordinate transformations of Maxwell’s equations

The technique of applying form-invariant, spatial coordinate transformations of Maxwell’s equations can facilitate the design of structures with unique electromagnetic or optical functionality. Here, we illustrate the transformation-optical approach in the designs of a square electromagnetic cloak and an omni-directional electromagnetic field concentrator. The transformation equations are described and the functionality of the devices is numerically confirmed by two-dimensional finite element simulations. The two devices presented demonstrate that the transformation optic approach leads to the specification of complex, anisotropic and inhomogeneous materials with well directed and distinct electromagnetic behavior.     

Solution conformational preferences of glutaric, 3‐hydroxyglutaric, 3‐methylglutaric acid,and their mono‐ and dianions

Conformational preferences of glutaric, 3‐hydroxyglutaric and 3‐methylglutaric acid, and their mono‐ and dianions have been investigated with the aid of NMR spectroscopy. In contrast to succinic acid, glutaric acid displays essentially statistical conformational equilibria in polar and non‐polar solutions of high and low hydrogen‐bonding ability with no clear evidence for intramolecular hydrogen‐bonding interactions. The acid ionization constant ratios, K ₁/K₂, in D₂O and DMSO of glutaric, 3‐hydroxyglutaric, and 3‐methylglutaric acids also indicate that intramolecular interactions are much less important than, or indeed insignificant, for shorter‐chain acids. FTIR studies on 3‐methylglutaric acid indicate some preference for either association with solvent or dimerization, depending on the solvent, rather than intramolecular hydrogen bonding. Copyright © 2008 John Wiley & Sons, Ltd.     

Surface chemistry of carbon dioxide

The review discusses how CO₂ surface chemistry has developed since the early 1950s. Emphasis is given to studies of well-characterized surfaces of metals, oxides and some more complex systems involving in particular alkali modified surfaces and also of coadsorbed molecules.     

The synthesis of the africane-type sesquiterpenoid, 1,5,8,8-tetramethyl-tricyclo[8,1,0,02,6]undec-5-en-9-ol-4-one

One of the alcohols derived from rearrangement of humulene-4,5-epoxide has been converted into a keto-alcohol, the angelate ester of which is a naturally-occurring sesquiterpenoid.     

13C and 77Se NMR spectra of thienoisoselenazoles,selenoloisothiazoles, selenoloisoselenazoles and thienoisothiazoles

Measurements are reported of NH exchange rates of urea, thiourea, acetamide and thioacetamide, using line-shape analysis with natural-abundance ¹⁵N NMR spectra. Base-catalyzed NH-proton exchange of thiourea is 30–40 times faster than for urea, while the corresponding acid-catalyzed exchange is 150 times slower. The base-catalyzed proton exchange for thioacetamide is about 1000 times faster than that of acetamide at 25°C, while the corresponding acid-catalyzed exchange is some 260 times slower.