For more than three decades the catalytic synthesis of acrylates from the cheap and abundantly available C(1) building block carbon dioxide and alkenes has been an unsolved problem in catalysis research, both in academia and industry. Herein, we describe a homogeneous catalyst based on nickel that permits the catalytic synthesis of the industrially highly relevant acrylate sodium acrylate from CO(2), ethylene, and a base, as demonstrated, at this stage, by a turnover number of greater than 10 with respect to the metal.
The nickel-catalyzed direct carboxylation of alkenes with the cheap and abundantly available C1 building block carbon dioxide (CO2 ) in the presence of a base has been achieved. The one-pot reaction allows for the direct and selective synthesis of a wide range of α,β-unsaturated carboxylates (TON>100, TOF up to 6 h(-1) , TON=turnover number, TOF=turnover frequency). Thus, it is possible, in one step, to synthesize sodium acrylate from ethylene, CO2 , and a sodium salt. Acrylates are industrially important products, the synthesis of which has hitherto required multiple steps.
A method for the synthesis of highly crystalline Rh2P nanoparticles on SiO2 support materials and their use as truly eterogeneous single-site catalysts for the hydroformylation of ethylene and propylene is presented. The supported Rh2P nanoparticles were investigated by transmission electron microscopy and by infrared analysis of adsorbed CO. The influence of feed gas composition and reaction temperature on the activity and selectivity in the hydroformylation reaction was evaluated by using high throughput experimentation as an enabling element; core findings were that beneficial effects on the selectivity were observed at high CO partial pressures and after addition of water to the feed gas. The analytical and performance data of the materials gave evidence that high temperature reduction leading to highly crystalline Rh2P nanoparticles is key to achieving active, selective, and longterm stable catalysts
Herein, we demonstrate the application of adducts of various N‐heterocyclic carbenes (NHCs) with CO2 (i.e., NHC–CO2) as precatalysts in the ring‐opening homopolymerization of propylene oxide (PO) onto diethylene glycol as a chain starter to give well‐defined polyether diols. The influence of various NHCs on the structure of the polymers and the mechanism of this reaction were investigated both experimentally and through DFT calculations. With this methodology, copolymers of PO and the monomers ε‐caprolactone and (S,S)‐lactide are accessible.
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