Rhenium Complexes Bearing Tridentate and Bidentate Phosphinoamine Ligands in the Production of Biofuel Alcohols via the Guerbet Reaction

We report a variety of rhenium complexes supported by bidentate and tridentate phosphinoamine ligands and their use in the formation of the advanced biofuel isobutanol from methanol and ethanol. Rhenium pincer complexes 1-3 are effective catalysts for this process, with 2 giving isobutanol in 35% yields, with 97% selectivity in the liquid fraction, over 16 h with catalyst loadings as low as 0.07 mol %. However, these catalysts show poorer overall selectivity, with the formation of a significant amount of carboxylate salt solid byproduct also being observed. Production of the active catalyst Id has been followed by P-31 NMR spectroscopy, and the importance of the presence of base and elevated temperatures to catalyst activation has been established. Complexes supported by diphosphine ligands are inactive for Guerbet chemistry; however, complexes supported by bidentate phosphinoamine ligands show greater selectivity for isobutanol formation over carboxylate salts. The novel complex 7 was able to produce isobutanol in 28% yield over 17 h. The importance of the N-H moiety to the catalytic performance has also been established, giving further weight to the hypothesis that these catalysts operate via a cooperative mechanism.

Automated summary

This study presents the utilization of rhenium complexes supported by phosphinoamine ligands as catalysts for isobutanol production, with complex 2 showing high efficiency in producing isobutanol at 35% yield. The formation of carboxylate salt byproduct was observed, highlighting the importance of factors influencing catalyst activity.