Reusable Copper Catechol‐based Porous Polymers for the Highly Efficient Heterogeneous Catalytic Oxidation of Secondary Alcohols

New catechol-based porous polymers were synthesized and used as platforms for the heterogenization of molecular Cu complexes. The resulting Cu@CatMP-1 materials proved to be highly stable and performing catalysts for the oxidation of secondary alcohols with turnover numbers up to 6000, about 1 to 2 orders of magnitude higher than the current relevant state of the art, using catalyst loadings as low as 25 ppm of Cu. The solid catalyst proved to be recyclable for over 10 runs without detectable metal leaching and has been scaled to the gram scale. The coordination of Cu to catechol within the polymer has been evidenced by X-ray absorption spectroscopy

X-ray Absorption Spectroscopy and Coherent X-ray Diffraction Imaging for Time-Resolved Investigation of the Biological Complexes: Computer Modelling towards the XFEL Experiment

The development of the next generation synchrotron radiation sources – free electron lasers – is approaching to become an effective tool for the time-resolved experiments aimed to solve actual problems in various fields such as chemistry, biology, medicine, etc. In order to demonstrate, how these experiments may be performed for the real systems to obtain information at the atomic and macromolecular levels, we have performed a molecular dynamics computer simulation combined with quantum chemistry calculations for the human phosphoglycerate kinase enzyme with Mg containing substrate. The simulated structures were used to calculate coherent X-ray diffraction patterns, reflecting the conformational state of the enzyme, and Mg K-edge X-ray absorption spectra, which depend on the local structure of the substrate. These two techniques give complementary information making such an approach highly effective for time-resolved investigation of various biological complexes, such as metalloproteins or enzymes with metal-containing substrate, to obtain information about both metal-containing active site or substrate and the atomic structure of each conformation

Copper–cobalt double metal cyanides as green catalysts for phosphoramidate synthesis

Abstract Phosphoramidates are common and widespread backbones of a great variety of fine chemicals, pharmaceuticals, additives and natural products. Conventional approaches to their synthesis make use of toxic chlorinated reagents and intermediates, which are sought to be avoided at an industrial scale. Here we report the coupling of phosphites and amines promoted by a Cu3[Co(CN)6]2-based double metal cyanide heterogeneous catalyst using I2 as additive for the synthesis of phosphoramidates. This strategy successfully provides an efficient, environmentally friendly alternative to the synthesis of these valuable compounds in high yields and it is, to the best of our knowledge, the first heterogeneous approach to this protocol. While the detailed study of the catalyst structure and of the metal centers by PXRD, FTIR, EXAFS and XANES revealed changes in their coordination environment, the catalyst maintained its high activity for at least 5 consecutive iterations of the reaction. Preliminary mechanism studies suggest that the reaction proceeds by a continuous change in the oxidation state of the Cu metal, induced by a O2/I− redox cycle

Olefins from Biobased Sugar Alcohols via Selective, Ru-Mediated Reaction in Catalytic Phosphonium Ionic Liquids

status: publishe

Dynamic Behavior of Pd/P4VP Catalyst during the Aerobic Oxidation of 2-Propanol: A Simultaneous SAXS/XAS/MS Operand Study

status: publishe