Annelated Pyridines as Highly Nucleophilic and Lewis Basic Catalysts for Acylation Reactions

New heterocyclic derivatives of 9‐azajulolidine have been synthesized and characterized with respect to their nucleophilicity and Lewis basicity. The Lewis basicity of these bases as quantified through their theoretically calculated methyl‐cation affinities correlate well with the experimentally measured reaction rates for addition to benzhydryl cations. All newly synthesized pyridines show exceptional catalytic activities in benchmark acylation reactions, which correlate only poorly with Lewis basicity or nucleophilicity parameters. A combination of Lewis basicity with charge and geometric parameters in the framework of a three‐component quantitative structure–activity relationship (QSAR) model is, however, highly predictive.     

Integration of the 1,2,3‐Triazole “Click” Motif as a Potent Signalling Element in Metal Ion Responsive Fluorescent Probes

In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D‐A) substituted 1,2,3‐triazoles as conjugative π‐linkers between the alkali metal ion receptor N‐phenylaza‐[18]crown‐6 and different fluorophoric groups with different electron‐acceptor properties (4‐naphthalimide, meso‐phenyl‐BODIPY and 9‐anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge‐transfer (CT) type probes 1 , 2 and 7 , the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge‐separated states. In the presence of Na⁺ and K⁺ ICT is interrupted, which resulted in a lighting‐up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7 , which contains a 9‐anthracenyl moiety as the electron‐accepting fluorophore, is the only probe which retains light‐up features in water and works as a highly K⁺/Na⁺‐selective probe under simulated physiological conditions. Virtually decoupled BODIPY‐based 6 and photoinduced electron transfer (PET) type probes 3 – 5 , where the 10‐substituted anthracen‐9‐yl fluorophores are connected to the 1,2,3‐triazole through a methylene spacer, show strong ion‐induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3‐triazole fluoroionophores.     

pH‐Dependent Coordination of AgI Ions by Histidine: Experiment,Theory, and a Model for SilE

Artificial implants and biomaterials lack the natural defense system of our body and, thus, have to be protected from bacterial adhesion and biofilm formation. In addition to the increasing number of implanted objects, the resistance of bacteria is also an important problem. Silver ions are well‐known for their antimicrobial properties, yet not a lot is known about their mode of action. Silver is expected to interact on many levels, thus the development of silver resistance is very difficult. Nevertheless, some bacteria are able to resist silver, even at higher concentrations. One such defense mechanism of bacteria against heavy‐metal intoxication includes an efflux system. SilE, a periplasmic silver‐binding protein that is involved in this defense mechanism, has been shown to possess numerous histidine functions, which strongly bind to silver atoms, as demonstrated by ourselves previously. Herein, we address the question of how histidine binds to silver ions as a function of pH value. This property is important because the local proton concentration in cells varies. Thus, we solved the crystal structures of histidine–silver complexes at different pH values and also investigated the influence of the amino‐acid configuration. These results were completed by DFT calculations on the binding strength and packing effects and led to the development of a model for the mode of action of SilE.     

The Ligand‐Based Quintuple Bond‐Shortening Concept and Some of Its Limitations

Herein, the ligand‐based concept of shortening quintuple bonds and some of its limitations are reported. In dichromium–diguanidinato complexes, the length of the quintuple bond can be influenced by the substituent at the central carbon atom of the used ligand. The guanidinato ligand with a 2,6‐dimethylpiperidine backbone was found to be the optimal ligand. The reduction of its chromium(II) chloride–ate complex gave a quintuply bonded bimetallic complex with a Cr? Cr distance of 1.7056 (12) Å. Its metal–metal distance, the shortest observed in any stable compound yet, is of essentially the same length as that of the longest alkane C? C bond (1.704 (4) Å). Both molecules, the alkane and the Cr complex, are of remarkable stability. Furthermore, an unsupported Cr^I dimer with an effective bond order (EBO) of 1.25 between the two metal atoms, indicated by CASSCF/CASPT2 calculations, was isolated as a by‐product. The formation of this by‐product indicates that with a certain bulk of the guanidinato ligand, other coordination isomers become relevant. Over‐reduction takes place, and a chromium–arene sandwich complex structurally related to the classic dibenzene chromium complex was observed, even when bulkier substituents are introduced at the central carbon atom of the used guanidinato ligand.     

Dual Gold Catalysis: σ,π‐Propyne Acetylide and Hydroxyl‐Bridged Digold Complexes as Easy‐To‐Prepare and Easy‐To‐Handle Precatalysts

A series of dinuclear gold σ,π‐propyne acetylide complexes were prepared and tested for their catalytic ability in dual gold catalysis that was based on the reaction of an electrophilic π‐complex of gold with a gold acetylide. The air‐stable and storable catalysts can be isolated as silver‐free catalysts in their activated form. These dual catalysts allow a fast initiation phase for the dual catalytic cycles without the need for additional additives for acetylide formation. Because propyne serves as a throw‐away ligand, no traces of the precatalyst are generated. Based on the fast initiation process, side products are minimized and reaction rates are higher for these catalysts. A series of test reactions were used to demonstrate the general applicability of these catalysts. Lower catalyst loadings, faster reaction rates, and better selectivity, combined with the practicability of these catalysts, make them ideal catalysts for dual gold catalysis.     

Carbon‐Coated LiTi2(PO4)3: An Ideal Insertion Host for Lithium‐Ion and Sodium‐Ion Batteries

We report the extraordinary performance of carbon‐coated sodium super ion conductor (NASICON)‐type LiTi₂(PO₄)₃ as an ideal host matrix for reversible insertion of both Li and Na ions. The NASICON‐type compound was prepared by means of a Pechini‐type polymerizable complex method and was subsequently carbon coated. Several characterization techniques such as XRD, thermogravimetric analysis (TGA), field‐emission (FE) SEM, TEM, and Raman analysis were used to study the physicochemical properties. Both guest species underwent a two‐phase insertion mechanism during the charge/discharge process that was clearly evidenced from galvanostatic and cyclic voltammetric studies. Unlike that of Li (≈1.5 moles of Li), Na insertion exhibits better reversibility (≈1.59 moles of Na) while experiencing a slightly higher capacity fade (≈8 % higher than Li) and polarization (780 mV) than Li. However, excellent rate capability profiles were noted for Na insertion relative to its counterpart Li. Overall, the Na insertion properties were found to be superior relative to Li insertion, which makes carbon‐coated NASICON‐type LiTi₂(PO₄)₃ hosts attractive for the development of next‐generation batteries.     

Validation of a coupled FE-model for the simulation of methane oxidation via thermal imaging

To simulate the processes of methane oxidation in landfill cover layers, a new computational model was created. The purpose of the model is to allow a forecast on the performance of methanotrophic activity in landfill cover layers under changing environmental conditions. Therefore, a thermodynamic consistent model based on the well-known Theory of Porous Media (TPM) combined with the mixture theory was developed, which analyzes the relevant gas productions of methane, oxygen and carbon dioxide. Diffusion, advection and conversion processes are considered as well as the energy production during methane oxidation. With the help of the thermal imaging technique a new experimental setup was developed in order to validate the coupled model in terms of the heat generation. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Characterisation of filled rubber with a pronounced non-linear viscoelasticity

This contribution presents the characterisation of an incompressible carbon black-filled elastomer as one characteristical example for highly filled rubber. It shows a strongly pronounced non-linear viscoelastic behaviour and the most important characteristic is the extremely long relaxation time which has to be taken into account. The material model is developed with respect to uniaxial tension data. The basis in the development of a phenomenological model is given by the basic elasticity. For this evaluation the long term relaxation behaviour results in a complex experimental procedure. Therefore, special attention has to be paid according to an optimised experimental process in order to get the necessary reference data in an adequate and reproduceable way [1]. With this model basis further investigations are taken into account concerning the time-dependent viscoelasticity. Therefore, cyclic deformations from zero up to a maximum of deformation are considered for different strain rates. Furthermore, the relaxation behaviour is investigated for multiple strain levels. The phenomena which are observed in the experimental results yield in a purely viscoelastic model, based on a rheological analogous model consisting of an equilibrium spring and several Maxwell-elements which contain nonlinear relations for the relaxation times of the dashpot elements [1,2]. The material model's numerical realisation is accomplished in two ways. Because of its numerical simplicity especially according to the parameter identification the model is restricted only to the simple case of uniaxial tension. A second, alternative implementation is executed providing the benefit that more complex deformation conditions can also be taken into account. Therefore, the general, three-dimensional finite model is implemented in an open-source Finite Element library [3]. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Borane Adducts of Aromatic Phosphorus Heterocycles: Synthesis,Crystallographic Characterization and Reactivity of a Phosphinine-B(C6F5)3 Lewis Pair

A phosphinine-borane adduct of a Me₃Si-functionalized phosphinine and the Lewis acid B(C₆F₅)₃ has been synthesized and characterized crystallographically for the first time. The reaction strongly depends on the nature of the substituents in the α-position of the phosphorus heterocycle. In contrast, the reaction of B₂H₆ with various substituted phosphinines leads to an equilibrium between the starting materials and the phosphinine–borane adducts that is determined by the Lewis basicity of the phosphinine. The novel phosphinine borane adduct ( 6 -B(C₆F₅)₃) shows rapid and facile insertion and [4+2] cycloaddition reactivity towards phenylacetylene. A hitherto unknown dihydro-1-phosphabarrelene is formed with styrene. The reaction with an ester provides a new, facile and selective route to 1-R-phosphininium salts. These salts then undergo a [4+2] cycloaddition in the presence of Me₃Si−C≡CH and styrene to cleanly form unprecedented derivatives of 1-R-phosphabarrelenium salts.