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Issue 18, 2020
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Efficient transfer hydrogenation of carbonate salts from glycerol using water-soluble iridium N-heterocyclic carbene catalysts

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Abstract

The transfer hydrogenation of CO2 and carbonates from biomass-derived alcohols, such as glycerol, to afford formic and lactic acid is a highly attractive path to valorizing two waste streams, and is significantly more thermodynamically favorable than direct carbonate hydrogenation. Expanding on our seminal report of the first homogeneous catalyst for this process, here we show that thermally-robust and water-soluble Ir(I) and Ir(III) N-heterocyclic carbene (NHC) complexes with sulfonate-functionalized wingtips are highly prolific and robust catalysts for carbonate transfer hydrogenation from glycerol, requiring no additives in aqueous media. The most prolific catalyst of the nine examined, [Ir(NHC-Ph-SO3)2CO2]Na (cat 7), effectively facilitates the reaction at low catalyst loading (10 ppm) at 150 °C using microwave or conventional heating. The cation of the carbonate salt significantly impacts catalytic activity, with highest activity observed with Cs2CO3 (27 850 and 13 350 TONs for lactate and formate respectively in 6 hours, compared to 15 400 and 8120 with K2CO3). Catalytic amounts of Cs+ were found to significantly enhance activity with K2CO3. Catalyst 7 is even more prolific with conventional heating under a positive N2 pressure, reaching TOFs of >3000 h−1 and >2100 h−1 respectively for lactate and formate with K2CO3. The high activity of this catalyst compared to non-sulfonated and cyclooctadiene analogs is attributed to a combination of catalyst solubility in aqueous media and presence of π-acceptor carbonyl ligands. A catalytic mechanism is proposed for 7 involving O–H oxidative addition of glycerol, β-hydride elimination, bicarbonate dehydroxylation, insertion and reductive elimination.

Graphical abstract: Efficient transfer hydrogenation of carbonate salts from glycerol using water-soluble iridium N-heterocyclic carbene catalysts

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Supplementary files

Article information


Submitted
10 Jun 2020
Accepted
12 Aug 2020
First published
20 Aug 2020

Green Chem., 2020,22, 6093-6104
Article type
Paper

Efficient transfer hydrogenation of carbonate salts from glycerol using water-soluble iridium N-heterocyclic carbene catalysts

D. Ainembabazi, K. Wang, M. Finn, J. Ridenour and A. Voutchkova-Kostal, Green Chem., 2020, 22, 6093
DOI: 10.1039/D0GC01958E

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