Computer-aided rational design of Fe(III)-catalysts for the selective formation of cyclic carbonates from CO2 and internal epoxides

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The catalytic mechanism of the cyclic carbonate formation reaction between CO2 and internal epoxides promoted by Fe-salen and the Kleij catalyst was examined in detail to better understand how the catalytic efficiency can be increased. Specifically, we aimed to make the catalyst more chemoselective towards forming cyclic carbonates and preventing the competing side reaction leading to polycarbonates via ring-opening polymerization. A few rational design principles were derived and first tested using computer models based on density functional theory. The most promising candidate that was identified in the computer model was then prepared and found to display significantly enhanced reactivity towards forming the cyclic carbonates, supporting the validity of the mechanistic insights deduced from the computer simulations. We propose that a cyclic carbonate is formed most efficiently via an inner-sphere mechanism where both the CO2 and epoxide substrates utilize the metal center for the key bond forming events. In contrast, the ring-opening polymerization uses an outer-sphere mechanism, where a carbonate attacks and ring-opens the epoxide bound to the metal without engaging the metal directly. These mechanistic differences are exploited to implement a chemoselective catalyst by enhancing the rate of the cyclic carbonate formation reaction while leaving the polymerization pathway largely unaffected.
Publisher
ROYAL SOC CHEMISTRY
Issue Date
2017-10
Language
English
Article Type
Article
Keywords

EFFECTIVE CORE POTENTIALS; DIAZA-COPE REARRANGEMENT; SOLVATION FREE-ENERGIES; ORGANIC CARBONATES; MOLECULAR CALCULATIONS; SALEN COMPLEXES; COPOLYMERIZATION REACTIONS; PROPYLENE-OXIDE; METAL-COMPLEXES; DIOXIDE

Citation

CATALYSIS SCIENCE & TECHNOLOGY, v.7, no.19, pp.4375 - 4387

ISSN
2044-4753
DOI
10.1039/c7cy01435j
URI
http://hdl.handle.net/10203/226921
Appears in Collection
CH-Journal Papers(저널논문)
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