Basic Promotors Impact Thermodynamics and Catalyst Speciation in Homogeneous Carbonyl Hydrogenation

Homogeneously catalyzed reactions often make use of additives and promotors that affect reactivity patterns and improve catalytic performance. While the role of reaction promotors is often discussed in view of their chemical reactivity, we demonstrate that they can be involved in catalysis indirectly. In particular, we demonstrate that...

Solvent-Assisted Ketone Reduction by a Homogeneous Mn Catalyst

The choice of a solvent and the reaction conditions often defines the overall behavior of a homogeneous catalytic system by affecting the preferred reaction mechanism and thus the activity and selectivity of the catalytic process. Here, we explore the role of solvation in the mechanism of ketone reduction using a model representative of a...

Metal-ligand cooperative activation of HX (X=H, Br, OR) bond on Mn based pincer complexes

Reversible dissociation of H−X bond (M−L+H−X→M(X)-L(H); (Formula presented.)) is an important step during pre-activation, catalysis and possible deactivation of acid-base cooperative pincer based transition metal catalysts (M−L). Herein we carried out a high-throughput computational investigation of the thermodynamic stability of different...

Manganese-Mediated C-C Bond Formation: Alkoxycarbonylation of Organoboranes

Alkoxycarbonylations are important and versatile reactions that result in the formation of a new C-C bond. Herein, we report on a new and halide-free alkoxycarbonylation reaction that does not require the application of an external carbon monoxide atmosphere. Instead, manganese carbonyl complexes and organo(alkoxy)borate salts react to form...

The Impact of Computational Uncertainties on the Enantioselectivity Predictions: A Microkinetic Modeling of Ketone Transfer Hydrogenation with a Noyori-type Mn-diamine Catalyst

Selectivity control is one of the most important functions of a catalyst. In asymmetric catalysis the enantiomeric excess (e.e.) is a property of major interest, with a lot of effort dedicated to developing the most enantioselective catalyst, understanding the origin of selectivity, and predicting stereoselectivity. Herein, we investigate the...

MEO SAR: System Concepts and Analysis

Existing microwave remote sensing instruments used for Earth observation face a clear tradeoff between spatial resolution and revisit times at global scales. The typical imaging capabilities of current systems range from daily observations at kilometer-scale resolutions provided by scatterometers to meter-scale resolutions at lower temporal...

Composition- and Condition-Dependent Kinetics of Homogeneous Ester Hydrogenation by a Mn-Based Catalyst

The reaction medium and conditions are the key parameters defining the efficiency and performance of a homogeneous catalyst. In the state-of-the-art molecular descriptions of catalytic systems by density functional theory (DFT) calculations, the reaction medium is commonly reduced to an infinitely diluted ideal solution model. In this work,...

Beam-Switch Wide-Swath Mode for Interferometrically Compatible Single-Pol and Quad-Pol SAR Products

Future spaceborne synthetic aperture radar (SAR) systems are expected to deliver enormous quantity of data. Accordingly, the observation plan becomes crucial for a proper allocation of the mission resources. A central challenge is to reduce the number of acquisitions by making the same image available for more applications. Here, a relevant...

The performance of 2D array detectors for light sheet based fluorescence correlation spectroscopy

Single plane illumination microscopy based fluorescence correlation spectroscopy (SPIM-FCS) is a new method for imaging FCS in 3D samples, providing diffusion coefficients, transport, flow velocities and concentrations in an imaging mode. SPIM-FCS records correlation functions over a whole plane in a sample, which requires array detectors for...

FPGA implementation of a 32x32 autocorrelator array for analysis of fast image series

With the evolving technology in CMOS integration, new classes of 2D-imaging detectors have recently become available. In particular, single photon avalanche diode (SPAD) arrays allow detection of single photons at high acquisition rates (? 100kfps), which is about two orders of magnitude higher than with currently available cameras. Here we...