A series of water-soluble half-sandwich [Cp*Rh(N^N)Cl] (Cp* = pentamethylcyclopentadiene, N^N-substituted 2,2'-bipyridine) complexes containing electron-donating substituents around the 2,2'-bipyridyl ligand were synthesized and fully characterized for the regioselective reduction of nicotinamide coenzyme (NAD). The influence of the positional effect of the substituents on the structural, electrochemical, and catalytic properties of the catalyst was systematically studied in detail. The catalytic efficiency of the substituted bipyridine Cp*Rh complexes are inversely correlated with their redox potentials. The 5,5'-substituted bipyridine Cp*Rh complex, which had the lowest reduction potential, most effectively regenerated NADH with a turnover frequency of 1100 h. Detailed kinetic studies on the generation of intermediate(s) provide valuable mechanistic insight into this catalytic cycle and help to direct the future design strategy of corresponding catalysts.
The use of zinc glutarate (ZnGA) as a heterogeneous catalyst for the copolymerization of epichlorohydrin, an epoxide with an electron-withdrawing substituent, and CO2 is reported. This catalyst shows the highest selectivity (98%) for polycarbonate over the cyclic carbonate in epichlorohydrin/CO2 copolymerization under mild conditions. The (epichlorohydrin-co-CO2 ) polymer exhibits a high glass transition temperature (Tg ), 44 °C, which is the maximum Tg value obtained for the (epichlorohydrin-co-CO2 ) polymer to date.
Globally, the elevation of carbon dioxide (CO2 ) levels due to the anthropogenic effect poses a serious threat to the ecosystem. Hence, it is important to control and/or mitigate the level of CO2 in the atmosphere, which necessitates novel tools. Herein, it is proposed to improve CO2 sequestration by using model complexes based on the enzyme carbonic anhydrase (CA) in aqueous tertiary amine medium. The effect of substituents on the model CA model complexes on CO2 absorption and desorption was determined by using a stopped-flow spectrophotometer to follow pH changes through coupling to pH indicator and a continuous stirred-tank reactor (CSTR). The CO2 hydration rate constants were determined under basic conditions and compound 6, which contained a hydrophilic group, showed the highest absorption or hydration levels of CO2 (2.860×10(3) L mol(-1) s(-1) ). In addition, CSTR results for the absorption and desorption of CO2 suggest that simple model CA complexes could be used in post-combustion processing.
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