Determining the Catalyst Properties That Lead to High Activity and Selectivity for Catalytic Hydrodeoxygenation with Ruthenium Pincer Complexes

Ten ruthenium pincer complexes were evaluated as catalysts for the hydrodeoxygenation (HDO) reaction on a lignin monomer surrogate, vanillyl alcohol. Four of these complexes are reported herein with the synthesis and full characterization data for all and single-crystal X-ray diffraction data for three complexes bearing OH/O–, NMe2, and Me substituents on the pincer. A systematic study of these CNC pincer complexes revealed that the π-donor substituent on the pyridine ring plays a key role in enhancing the yield of the desired deoxygenated product. While OMe, OH, and NMe2 are all effective as π-donor substituents on the central pyridine ring in the pincer, the highest conversion to products and the best selectivity was observed with OH substituents and added sodium carbonate as a base. Base serves to deprotonate the OH group and form 1O- as observed spectroscopically. Furthermore, efforts to use other catalysts have revealed that free or labile sites are needed on the ruthenium center and an electronicall...