CNN Pincer Ruthenium Complexes for Efficient Transfer Hydrogenation of Biomass-Derived Carbonyl Compounds
The ligand HCNNOMe (6-(4-methoxyphenyl)-2-aminomethylpyridine) is easily prepared from the commercially available 6-(4-methoxyphenyl)pyridine-2-carbaldehyde by reaction of hydroxylamine and hydrogenation (H2, 1 atm) with Pd/C. The pincer complexes cis-[RuCl(CNNOMe)(PPh3)2] (1) and [RuCl(CNNOMe)(PP)] (PP = dppb, 2; dppf, 3) are synthesized from [RuCl2(PPh3)3], HCNNOMe and PP (for 2, 3) in 2-propanol with NEt3 at reflux and are isolated in 85-93% yield. Carbonylation of 1 (CO 1 atm) gives [RuCl(CNNOMe)(CO)(PPh3)] (4) (79% yield) which cleanly reacts with Na[BArf4] and PCy3, affording the cationic trans-[Ru(CNNOMe)(CO)(PCy3)(PPh3)][BArf4] (5) (92% yield). These robust pincer complexes display remarkably high catalytic activity in the transfer hydrogenation (TH) of lignocellulose biomass carbonyl compounds, using 2-propanol at reflux in basic media (NaOiPr, K2CO3). Thus, furfural, 5-(hydroxymethyl)furfural and Cyrene are reduced to the corresponding alcohols with 2 and 3, at S/C in the range of 10000-100000, within minutes or hours (TOF up to 1500000 h-1). The monocarbonyl complex 5 was found extremely active in the TH of cinnamaldehyde, vanillin derivatives and ethyl levulinate at S/C of 10000-50000. Vanillyl alcohol is also obtained by TH of vanillin with 5 (S/C = 500) in 2-propanol in the presence of K2CO3.