C2v-symmetric metalloporphyrin promoted cycloaddition of epoxides with CO2 under atmospheric pressure. (January 2019)

• Record Type: Journal Article
• Authors: Jiang, Xu; Gou, Faliang; Qi, Chenze
• Is Part Of: Journal of CO₂ utilization. Volume 29(2019)
• Page Start: 134
• Page End: 139
• Publication Date: 2019-01
• Subjects: CO2 fixation -- Metalloporphyrin -- Cyclic carbonates -- Kinetic study -- Atmospheric pressure; Carbon dioxide -- Periodicals; Carbon dioxide -- Environmental aspects -- Periodicals; Carbon dioxide mitigation -- Periodicals; Carbon dioxide; Carbon dioxide -- Environmental aspects; Carbon dioxide mitigation; Periodicals; 628.53205
• DOI: 10.1016/j.jcou.2018.12.003
• Languages: English
• ISSNs: 2212-9820

Abstract

Graphical abstract: Highlights: C2 v -symmetric metalloporphyrins were synthesized for the cycloaddition of epoxides and CO2 at atmospheric pressure. The catalytic performance is strongly dependent on their coordinated metal species of catalysts. Detailed kinetic investigations were carried out by three catalysts. A Lewis acid-base dual cooperative catalytic mechanism was carefully proposed. Abstract: A series of C2 v -symmetric diphenylporphyrin complexes containing a metal ion (Mg, Al, Mn, Fe, Co, Zn) have been synthesized and applied as catalysts for the solvent-free cycloaddition of epoxides and carbon dioxide under atmospheric pressure and mild temperature, in concert with phenyltrimethylammonium tribromide (PTAT) as a co-catalyst. The activity of these catalysts deeply relies on their coordinated metal species. [5, 15-Diphenylporphyrin]manganese(III) chloride (DPP-MnCl ) has been found to be the most effective catalyst under optimal reaction conditions. It's worth mentioning that the cycloaddition of phenyl glycidyl ether (GPE) and CO2 proceeded successfully byDPP-MnCl /PTAT even at 25 °C and atmospheric pressure. Moreover, preliminary kinetic investigations of this cycloaddition were carried out by using catalystsDPP-MnCl, DPP-CoCl andDPP-Zn, revealing that the (phenoxymethyl)ethylene carbonate (PEC) formation with the lowest activation energy is catalyzed byDPP-MnCl . Furthermore, a Lewis acid-base dual cooperative catalytic mechanism has been carefully proposed in light of the catalyst systems and the experimental results.