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Manganese diphosphine and phosphinoamine complexes are effective catalysts for the production of biofuel alcohols via the Guerbet reaction

King, Ashley M., Sparkes, Hazel A., Wingad, Richard L. and Wass, Duncan F. 2020. Manganese diphosphine and phosphinoamine complexes are effective catalysts for the production of biofuel alcohols via the Guerbet reaction. Organometallics 39 (21) , pp. 3873-3878. 10.1021/acs.organomet.0c00588

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Abstract

We report a variety of manganese-based catalysts containing both chelating diphosphine (bis(diphenylphosphino)methane (dppm: 1, 2, and 7) or 1,2-bis(diphenylphosphino)ethane (dppe: 3)), and mixed-donor phosphinoamine (2-(diphenylphosphino)ethylamine (dppea: 4–6)) ligands for the upgrading of ethanol and methanol to the advanced biofuel isobutanol. These catalysts show moderate selectivity up to 74% along with turnover numbers greater than 100 over 90 h, with catalyst 2 supported by dppm demonstrating superior performance. The positive effect of substituting the ligand backbone was also displayed with a catalyst supported by C-phenyl-substituted dppm (8) having markedly improved performance compared to the parent dppm catalysts. Catalysts supported by the phosphinoamine ligand dppea are also active for the upgrading of ethanol to n-butanol. These results show that so-called PNP-pincer ligands are not a prerequisite for the use of manganese catalysts in Guerbet chemistry and that simple chelates can be used effectively.

Item Type: Article
Date Type: Publication
Status: Published
Schools: Chemistry
Cardiff Catalysis Institute (CCI)
Publisher: American Chemical Society
ISSN: 0276-7333
Funders: EPSRC and BP
Date of First Compliant Deposit: 3 December 2020
Date of Acceptance: 12 October 2020
Last Modified: 13 Jan 2021 15:13
URI: http://orca.cardiff.ac.uk/id/eprint/136750

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