The Fluorenyl Cation

The fluorenyl cation is a textbook example for a 4π antiaromatic cation. However, contrasting results have been published on how the annelated benzene rings compensate the destabilizing effect of the 4π antiaromatic five‐membered ring in its core. Whereas previous attempts to synthesize this cation in superacidic media resulted in undefined polymeric material only, we herein report that it can be generated and isolated in amorphous water ice at temperatures below 30 K by photolysis of diazofluorene. Under these conditions, the fluorenylidene is protonated by water to give the fluorenyl cation, which could be characterized spectroscopically. Its absorption in the visible‐light range matches that previously obtained by ultrafast absorption spectroscopy, and furthermore, its IR spectrum could be recorded. The IR bands in amorphous ice very nicely match predictions from DFT and DFT/MM calculations, suggesting the absence of strong interactions between the cation and surrounding water molecules.     

Spin-State Variations of Iron(III) Complexes with Tetracarbene Macrocycles

Starting from their six-coordinate iron(II) precursor complexes [L^8RFe(MeCN)]²⁺, a series of iron(III) complexes of the known macrocyclic tetracarbene ligand L^8H and its new octamethylated derivative L^8Me, both providing four imidazol-2-yliden donors, were synthesized. Several five- and six-coordinate iron(III) complexes with different axial ligands (Cl⁻, OTf⁻, MeCN) were structurally characterized by X-ray diffraction and analyzed in detail with respect to their spin state variations, using a bouquet of spectroscopic methods (NMR, UV/Vis, EPR, and ⁵⁷Fe Mößbauer). Depending on the axial ligands, either low-spin (S=1/2) or intermediate-spin (S=3/2) states were observed, whereas high-spin (S=5/2) states were inaccessible because of the extremely strong in-plane σ-donor character of the macrocyclic tetracarbene ligands. These findings are reminiscent of the spin state patterns of topologically related ferric porphyrin complexes. The ring conformations and dynamics of the macrocyclic tetracarbene ligands in their iron(II), iron(III) and μ-oxo diiron(III) complexes were also studied.     

Control of the electrode temperature for electrochemical studies: A new approach illustrated on porous anodizing of aluminium

A new approach for studying the effect of temperature on electrochemical processes is presented in this paper. Using an in-house developed electrode holder, experiments are performed under conditions of applied and controlled electrode temperature. This new approach provides an improved temperature control during the experimental study and, additionally, allows distinguishing both the influences of the electrolyte and electrode temperatures. The advantages of the applied electrode temperature approach are illustrated by considering porous anodizing of aluminium. In a broad temperature range the electrochemical behaviour of the aluminium electrodes, recorded during the new and the conventional way of anodizing, are compared. Differences between the anodic potential evolutions in both approaches are observed, and are explained by a heat flux to the surroundings during the experiments at uncontrolled electrode temperature. These results illustrate the advantage of applying the electrode temperature. If the influence of temperature on a process is investigated by merely varying the electrolyte temperature, the electrode temperature is only indirectly influenced and can significantly differ from the electrolyte temperature. Therefore, when evaluating the influence of temperature on an electrochemical system the electrode temperature should be considered, and preferentially also controlled.     

Synthesis of the bis-potassium salts of 5-hydroxy-3-oxopent-4-enoic acids and their use for the efficient preparation of 4-hydroxy-2H-pyran-2-ones and other heterocycles

5-Hydroxy-3-oxopent-4-enoic acid esters can be efficiently transformed into the stable bis-potassium salts of the corresponding 5-hydroxy-3-oxopent-4-enoic acids, from which the sensitive acids are released in situ, the latter being converted into substituted 4-hydroxy-2H-pyran-2-ones, pyrazoles and isoxazoles under mild conditions; the efficiency of this method is demonstrated by the first synthesis of two naturally occurring pyrones.     

Iron porphyrins catalyze the synthesis of non-protected amino acid esters from ammonia and diazoacetates

Iron complexes of porphyrins (and corroles to a lesser extent) are the first catalysts to utilize ammonia for the synthesis of N-free amino acid esters.