Heterogeneous Olefin Hydrogenation Enabled by a Highly-Reduced Nickel(-II) Catalyst Precursor.

Invited for the cover of this issue is the group of Robert Wolf at the University of Regensburg and colleagues at the University of Hamburg. The image depicts the hydrogenation of triphenylethylene. Read the full text of the article at 10.1002/chem.201905537.

Heterogeneous Olefin Hydrogenation Enabled by a Highly-Reduced Nickel(-II) Catalyst Precursor.

The hydrogenation of olefins, styrenes, enoates, imines, and sterically hindered tri-substituted olefins was accomplished using the pre-catalyst dilithiumbis(cycloocta-1,5-diene)nickelate(-II) (1). The mild conditions tolerate hydroxyl, halide, ester, and lactone functionalities. Mechanistic studies, including reaction progress analyses, poisoning experiments, and multinuclear NMR monitoring, indicate that a heterotopic (nickel nanoparticle) catalyst is in operation.

Introducing a non-pixelated and fast centre of mass detector for differential phase contrast microscopy.

With the advent of probe corrected STEM machines it became possible to probe specimens on a scale of less than 50 pm resolution. This opens completely new horizons for research, as it is e.g. possible to probe the electrostatic fields between individual rows of atoms, using differential phase contrast (DPC). However, in contrast to conventional DPC, where one deals with extended fields which can be assumed constant across the electron probe, this is not possible for sub-atomic probes in DPC. For the latter case it was shown [1,2], that the strongly inhomogeneous field distribution within the probe diameter, which usually is caused by the nuclear potentials of an atomic column, leads to a complicated intensity redistribution within the diffraction disk. The task is then to determine the intensity weighted centre of the diffraction disk pattern (frequently also called centre of mass, COM), which is proportional to the average lateral momentum gained by the average electron, transmitted through the probe diameter. In first reported measurements, the determination of this COM was achieved using a pixelated detector in combination with a software-based evaluation of the COM. This suffers from two disadvantages: first, the nowadays available pixelated detectors are still not very fast (approximately 1000 fps) and quite expensive, and second, the amount of data to be processed after acquisition is comparatively huge. In this paper we report on an alternative to a pixelated detector, which is able to directly deliver the COM of a diffraction disk's intensity distribution with frequencies up to 200 kHz. We present measurements on the sensitivity of this detector as well as first results from DPC imaging. From these results we expect the detector also to serve well in sub-atomic DPC field sensing, possibly replacing today's segmented or pixelated detectors.

On the achievable field sensitivity of a segmented annular detector for differential phase contrast measurements.

Differential phase contrast microscopy measures minute deflections of the electron probe due to electric and/or magnetic fields, using a position sensitive device. Although recently, pixelated detectors have become available which also serve as a position sensitive device, the most frequently used detector is a four-segmented annular semiconducting detector ring (or variations thereof), where the difference signals of opposing detector elements represent the components of the deflection vector. This deflection vector can be used directly to quantitatively determine the deflecting field, provided the specimen's thickness is known. While there exist many measurements of both electric and magnetic fields, even at an atomic level, until now the question of the smallest clearly resolvable field value for this detector has not yet been answered. This paper treats the problem theoretically first, leading to a calibration factor κ which depends solely on simple, experimentally accessible parameters and relates the deflecting field to the measured deflection vector. In a second step, the calibration factor for our combination of microscope and detector is determined experimentally for various combinations of camera length, condenser aperture and spot size to determine the optimum setup. From this optimized condition we determine the minimum change in field which leads to a clearly measurable signal change for both HMSTEM and LMSTEM operation. A strategy is described which allows the experimenter to choose the setup giving the highest field sensitivity. Quantification problems due to scattering processes in the specimen are addressed and ways are shown to choose a setup which is less sensitive to these artefacts.