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Benefit of a Hemilabile Ligand in Deoxygenation of Fatty Acids to 1-Alkenes

Abstract

One of the most important tasks for chemistry in our time is to contribute to sustainable chemical production. A green industrial process for linear α-olefins, the arguably most important class of petrochemical intermediates, from renewable resources would be a major contribution to this end. Plant oils are attractive renewable feedstocks for this purpose because their triglycerides can be hydrolyzed to fatty acids that contain valuable long-chain hydrocarbons (C16-C22). These hydrocarbons, may, in turn be converted to α-olefins by deoxygenation of the fatty acids. For the most selective of these deoxygenation reactions, transition-metal catalyzed decarbonylative dehydration, density functional theory (DFT) calculations have just started to offer valuable mechanistic insight, and the use of this insight in rational catalyst design has been facilitated by the arrival of the first well-defined precatalyst for this reaction, Pd(cinnamyl)Cl(DPEphos) (1). Here, we present DFT calculations showing how, in 1, the hemilability of DPEphos, a classical P-O-P diphosphine, contributes to a low overall barrier and high α-selectivity. DPEphos facilitates decarbonylation by first switching from bidentate to monodentate binding to create a coordination site for CO. Recoordination of the dangling phosphine displaces the Pd-bound CO, a co-product that must leave the reactor for the reaction to proceed, and the escaping CO is here modelled by using a low pressure in the calculation of its thermochemical corrections. Finally, the role of the hemilabile ligand suggests that further improvements in decarbonylative dehydration of fatty acids to α-olefins might be achieved by exploring new, potentially asymmetric, hemilabile ligands.

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Publication details

The article was received on 15 Apr 2019, accepted on 04 Jun 2019 and first published on 05 Jun 2019


Article type: Paper
DOI: 10.1039/C9FD00037B
Faraday Discuss., 2019, Accepted Manuscript

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    Benefit of a Hemilabile Ligand in Deoxygenation of Fatty Acids to 1-Alkenes

    S. H. Hopen Eliasson and V. R. Jensen, Faraday Discuss., 2019, Accepted Manuscript , DOI: 10.1039/C9FD00037B

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