Work

Ethanol Upgrading with N,N,N -Pincer-Based Ru Catalysts: Delineating Key Factors Governing Catalyst Evolution and Stability

Year: 2024

Type: article

Abstract: The 5-CH 3 -bpi (bpi = 1,3-bis(2′-pyridylimino)isoindolate) ruthenium catalyst is among the most active catalysts to generate higher order alcohols from ethanol, via the Guerbet reaction, yet the reason(s) for this beneficial CH 3 -subsitution position (5- relative to 4- and 6-) were not known. To understand the influence of this unique positional activity, we report a mechanistic investigation of the N,N,N- pincer Ru(bpi)(PPh 3 ) 2 Cl catalyst. In situ IR and ex situ NMR/ESI-MS analyses of catalytic reactions identified a series of Ru carbonyl species generated during catalysis. We find that the primary decomposition pathway is via hydrogenolysis of the bpi ligands and that incorporating a methyl group at the 5-position disfavors this deactivation pathway.

Source: ACS Catalysis

DOI: 10.1021/acscatal.4c01361

Authors: Benjamin M. Farris, Alex M. Davies, Corey R. J. Stephenson, Nathaniel K. Szymczak

Institution: University of Michigan

Language: English

Topic: Asymmetric Hydrogenation and Catalysis

Subfield: Inorganic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Camille and Henry Dreyfus Foundation, Basic Energy Sciences

Award: G6395224855