Novel phenylazole ligands were applied successfully in the synthesis of cyclometalated iridium(III) complexes of the general formula [Ir(phenylazole)(2)(bpy)]PF(6) (bpy=2,2'-bipyridine). All complexes were fully characterized by NMR, IR, and MS spectroscopic studies as well as by cyclic voltammetry. Three crystal structures obtained by X-ray analysis complemented the spectroscopic investigations. The excited-state lifetimes of the iridium complexes were determined and showed to be in the range of several hundred ns to multiple µs. All obtained iridium complexes were active as photosensitizers in catalytic hydrogen evolution from water in the presence of triethylamine as a sacrificial reducing agent. Applying an in situ formed iron-based water reduction catalyst derived from [HNEt(3)](+) [HFe(3)(CO)(11)](-) and tris[3,5-tris-(trifluoromethyl)-phenyl]phosphine as the ligand, [Ir(2-phenylbenz-oxazole)(2)-(bpy)]PF(6) proved to be the most efficient complex giving a quantum yield of 16% at 440 nm light irradiation.

Carbon dioxide can be used in various ways as a cheap C1 source. However, the utilization of CO2 requires energy or energy-rich reagents, which leads to further emissions, and therefore, diminishes the CO2-saving potential. Therefore, life cycle assessment (LCA) is required for each process that uses CO2 to provide valid data for CO2 savings. Carbon dioxide can be incorporated into epoxidized fatty acid esters to provide the corresponding carbonates. A robust catalytic process was developed based on simple halide salts in combination with a phase-transfer catalyst. The CO2-saving potential was determined by comparing the carbonates as a plasticizer with an established phthalate-based plasticizer. Although CO2 savings of up to 80 % were achieved, most of the savings arose from indirect effects and not from CO2 utilization. Furthermore, other categories have been analyzed in the LCA. The use of biobased material has a variety of impacts on categories such as eutrophication and marine toxicity. Therefore, the benefits of biobased materials have to be evaluated carefully for each case. Finally, interesting properties as plasticizers were obtained with the carbonates. The volatility and water extraction could be improved relative to the epoxidized system.

Light on the water: The coupling of Raman and EPR spectroscopy was crucial in the study of the activation, operation, and deactivation steps in the light‐driven splitting of water catalyzed by iridium and iron. The results may provide the foundation for improved water‐reduction catalysts. IrPS=iridium photosensitizer, TEA=triethylamine.

Evaluation of the long-term stability of electrocatalysts is typically performed using galvanostatic polarization at a predefined current density. A stable or insignificant increase in the applied potential is usually interpreted as high long-term stability of the tested catalyst. However, effects such as (i) electrochemical degradation of a catalyst due to its oxidation, (ii) blocking of the catalyst surface by evolved gas bubbles, and (iii) detachment of the catalyst from the electrode surface may lead to a decrease of the catalyst's active surface area being exposed to the electrolyte. In order to separate these effects and to evaluate the true electrochemical degradation of electrocatalysts, an advanced evaluation protocol based on subsequently performed electrochemical impedance, double layer capacitance, cyclic voltammetry, and galvanostatic polarization measurements was developed and used to evaluate the degradation of IrO2 particles drop-coated on glassy carbon rotating disk electrode using Nafion as a binder. A flow-through electrochemical cell was developed enabling circulation of the electrolyte leading to an efficient removal of evolved oxygen bubbles even at high current densities of up to 250 mA/cm(2). The degradation rate of IrO2 was evaluated over 225 test cycles (0.733 ± 0.022 mV/h) with a total duration of galvanostatic polarization measurements of over 55 h.

The reaction mechanism of CO2 coupling with C2H4 by homogeneous Ni‐complexes bearing bidentate phosphorous ligands was studied by means of density functional theory calculations. The reaction is initiated by sequential coordination of C2H4 and CO2 to the Ni center, followed by a facile coupling step, which results in a stable nickelalactone intermediate. Subsequent decomposition of this intermediate through β‐H transfer is the rate‐determining step. Together with the following reductive elimination step to form acrylic acid they represent a strongly kinetically‐hampered process. Destabilization of the nickelalactone intermediate in the presence of large bite angle bidentate ligands has only a minor effect on the overall reaction energetics. Modifying the electronic properties of ligands is also not effective to drive the reaction in a catalytic manner. These studies indicate that the coupling reaction has to be enforced through an alternative route. It is predicted here that a base‐assisted decomposition of the nickelalactone intermediate represents a favorable reaction channel. The factors affecting the reactivity of this route are investigated. The best reactivity corresponds to the CH3OH‐solvated CH3ONa that allows the β‐H transfer step to proceed with a barrier of only 49 kJ mol−1.

The stoichiometric reaction of [Rh(COD)Cl](2) with the anion resulting from the deprotonation of dppm(BH(3))(2) yielded a new alkyl Rh(I) complex; the coordination modes of the BH(3) groups are discussed on the basis of X-ray data, variable temperature multinuclear NMR experiments and DFT studies.

A bulky phosphabarrelene ligand is used in the platinum-catalyzed hydrosilylation of alkynes. High regioselectivities were achieved under mild conditions from an in situ formed catalyst at low catalyst loadings. Furthermore, a rare 14-VE PtL2 complex was isolated, which equally proved to be a highly reactive catalyst precursor.

International audienceCross-coupling reactions can be efficiently catalyzed using palladium complexes. The formation of low-coordinated, highly reactive Pd(0), which is believed to be the catalytic species, is critical. The mechanism of the reduction of a stable and readily available allyl Pd(II) complex into Pd(0) by a combination of K2CO3 and PhB(OH)2 has been studied. We report on the characterization of the associated reactive solution using a combination of density functional theory and experimental methods. First, the stoichiometric reaction of an (allyl)(phosphine)palladium(II) complex with K2CO3 was first investigated using trandem mass spectrometry. A palladium-carbonate complex could be characterized in the electrospray mass spectrum of the reactive solution. Gas-phase infrared spectra of mass-selected complexes have been recorded, giving further information on the coordination mode (κ1) of the carbonate ligand. This structural information derived from spectroscopy is critical because the relative energy of the two κ1- and κ2-carbonate isomers is difficult to determine theoretically, presumably because of the charge transfers at play between the carbonate and the palladium. Second, the product of the stoichiometric addition of PhB(OH)2 to this carbonate complex was investigated. Both 31P and 1H NMR data provide compelling evidence for the formation of the desired 14-electron Pd(0) complex