Peroxide Coordination of Tellurium in Aqueous Solutions

Tellurium–peroxo complexes in aqueous solutions have never been reported. In this work, ammonium peroxotellurates (NH₄)₄Te₂(μ‐OO)₂(μ‐O)O₄(OH)₂ ( 1 ) and (NH₄)₅Te₂(μ‐OO)₂(μ‐O)O₅(OH)?1.28 H₂O?0.72 H₂O₂ ( 2 ) were isolated from 5 % hydrogen peroxide aqueous solutions of ammonium tellurate and characterized by single‐crystal and powder X‐ray diffraction analysis, by Raman spectroscopy and thermal analysis. The crystal structure of 1 comprises ammonium cations and a symmetric binuclear peroxotellurate anion [Te₂(μ‐OO)₂(μ‐O)O₄(OH)₂]^4?. The structure of 2 consists of an unsymmetrical [Te₂(μ‐OO)₂(μ‐O)O₅(OH)]^5? anion, ammonium cations, hydrogen peroxide, and water. Peroxotellurate anions in both 1 and 2 contain a binuclear Te₂(μ‐OO)₂(μ‐O) fragment with one μ‐oxo‐ and two μ‐peroxo bridging groups. ¹²⁵Te NMR spectroscopic analysis shows that the peroxo bridged bitellurate anions are the dominant species in solution, with 3–40 %wt H₂O₂ and for pH values above 9. DFT calculations of the peroxotellurate anion confirm its higher thermodynamic stability compared with those of the oxotellurate analogues. This is the first direct evidence for tellurium–peroxide coordination in any aqueous system and the first report of inorganic tellurium–peroxo complexes. General features common to all reported p‐block element peroxides could be discerned by the characterization of aqueous and crystalline peroxotellurates.     

Reversible Phosphorylation of Trimethylsilylisothiocyanate

Abstract

The reaction of trimethylsilylisothiocyanate with phosphorus acids chlorides was demonstrated to be reversible.     

Heterocyclization of electrophilic alkenes with tetranitromethane revisited: regiochemistry and the mechanism of nitroisoxazole formation

Revised regiochemistry for the heterocyclization of electrophilic alkenes with tetranitromethane (TNM) in the presence of triethylamine, providing rapid access to nitroisoxazoles, is reported. The formation of 5-nitroisoxazoles previously incorrectly assigned as 3-nitro regioisomers, has now been established unambiguously by X-ray crystallography. Empirical computations with ACD/CNMR Predictor, based both on hierarchical ordering of spherical environments (HOSE) and an algorithm of artificial neural networks (ANN), and also Density Functional Theory computations of the ¹³C NMR chemical shifts for the 3- versus 5-nitroisoxazoles are shown to consistently match the spectra of the experimentally observed 5-regioisomers.     

Simulation of a mixed-conducting membrane-based gas turbine power plant for CO<Subscript>2</Subscript> capture: system level analysis of operation stability and individual process unit degradation

A gas turbine power plant for CO₂ capture, based on oxygen-permeable membranes with mixed ionic-electronic conductivity, was analysed with respect to long-term stability by means of numerical simulation. Due to the attractive transport and physicochemical properties of mixed-conducting La₂NiO_4+δ, this nickelate was selected as a prototype membrane material for this application. Experiments showed very slow degradation of La₂NiO_4+δ membranes at oxygen chemical potentials close to atmospheric conditions, which are associated with kinetic demixing and other microstructure-related factors. Interaction with CO₂ in the intermediate temperature range also leads to lower oxygen permeation, whilst increasing oxygen pressure may cause partial phase decomposition and microstructural changes, thus again limiting the range of possible operation conditions. The relevant operational constraints were included in a detailed membrane-based gas turbine power plant model. The membrane performance degradation with time was approximated by a linear function with average rate of 3.3% per 1,000 operation hours. Furthermore, performance deterioration of the gas turbine compressor and turbine were also considered. Simulations revealed that the power plant is substantially affected by degradation of the ceramic membranes and turbomachinery components. The already rather small operating window was further narrowed when compared with a conventional gas turbine power plant. Two different designs of the membrane-based power plant were analysed: (1) with and (2) without additional combustors (afterburners) between the membrane reactor and the gas turbine. Afterburners increase thermal efficiency as well as power output, but also lead to non-negligible CO₂ emissions. In order to have a frame of comparison, results for a conventional gas turbine power plant with degradation of turbomachinery components are also presented. Simulations representing changes in ambient temperature and fuel composition as well as failure incidents were executed to analyse the susceptibility of the gas turbine power plant to external and internal changes.     

Boundary behaviour of the mappings satisfying generalized inverse modular inequalities

We study the geometric properties of the mappings for which generalized inverse modular inequalities hold. We generalize in this way known theorems from the theory of analytic mappings and the theory of quasiregular mappings, like the theorems of Fatou, M. and F. Riesz, Beurling and Lindelöf and their extensions given for quasiregular mappings by Martio, Rickman and Vuorinen.     

Phosphorylation of Conjugated Enamines

Abstract

Introduction of benzylidene group at α-position of enamines derived from cyclic ketones substantially increases strength of C-P bond thus permitting further syntheses without splitting of the C-P bond. A wide set of phosphorylated derivatives of type (I) were prepared and their properties were studied. Combination of an enamine moiety with other nucleophilic centers such as C or N in a molecule allows to carry out cyclisation giving five- and six-membered phosphorus-containing heterocycles of types (II, III).