Jump to main content
Jump to site search
PLANNED MAINTENANCE Close the message box

Scheduled maintenance work on Wednesday 27th March 2019 from 11:00 AM to 1:00 PM (GMT).

During this time our website performance may be temporarily affected. We apologise for any inconvenience this might cause and thank you for your patience.

Issue 2, 2016
Previous Article Next Article

Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism

Author affiliations


The scope and mechanism of thermodynamically leveraged ester RC(O)O–R′ bond hydrogenolysis by tandem metal triflate + supported Pd catalysts are investigated both experimentally and theoretically by DFT and energy span analysis. This catalytic system has a broad scope, with relative cleavage rates scaling as, tertiary > secondary > primary ester at 1 bar H2, yielding alkanes and carboxylic acids with high conversion and selectivity. Benzylic and allylic esters display the highest activity. The rate law is ν = k[M(OTf)n]1[ester]0[H2]0 with an H/D kinetic isotope effect = 6.5 ± 0.5, implying turnover-limiting C–H scission following C–O cleavage, in agreement with theory. Intermediate alkene products are then rapidly hydrogenated. Applying this approach with the very active Hf(OTf)4 catalyst to bio-derived triglycerides affords near-quantitative yields of C3 hydrocarbons rather than glycerol. From model substrates, it is found that RC(O)O–R′ cleavage rates are very sensitive to steric congestion and metal triflate identity. For triglycerides, primary/external glyceryl CH2–O cleavage predominates over secondary/internal CH–O cleavage, with the latter favored by less acidic or smaller ionic radius metal triflates, raising the diester selectivity to as high as 48% with Ce(OTf)3.

Graphical abstract: Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism

Back to tab navigation

Supplementary files

Publication details

The article was received on 23 Oct 2015, accepted on 26 Nov 2015 and first published on 26 Nov 2015

Article type: Paper
DOI: 10.1039/C5EE03256C
Author version
Download author version (PDF)
Citation: Energy Environ. Sci., 2016,9, 550-564

  •   Request permissions

    Mono- and tri-ester hydrogenolysis using tandem catalysis. Scope and mechanism

    T. L. Lohr, Z. Li, R. S. Assary, L. A. Curtiss and T. J. Marks, Energy Environ. Sci., 2016, 9, 550
    DOI: 10.1039/C5EE03256C

Search articles by author