Ruthenium p-cymene complexes with α-diimine ligands as catalytic precursors for the transfer hydrogenation of ethyl levulinate to γ-valerolactone

The ruthenium compounds [(η6-p-cymene)RuCl{κ2N-(HCNR)2}]NO3 (R = 4-C6H4Me, [1]NO3; 4-C6H4OH, [2]NO3; C6H11Cy, [3]NO3; 4-C6H10OH, [4]NO3; tBu, [5]NO3) were prepared in high yields from [(p-cymene)RuCl2]2, AgNO3 and the appropriate α-diimine. Compounds [2]PF6 and [4]PF6 were obtained by a straightforward reaction of [(η6-p-cymene)RuCl(MeCN)0.66]PF6, [6]PF6, with α-diimine, whereas [4]BPh4 was obtained by metathesis between [4]NO3 and NaBPh4. All the ruthenium products were characterized by analytical methods, IR, NMR and UV-Vis spectroscopy; in addition, the structure of [1]NO3 was ascertained by an X-ray diffraction study. Compounds [1–4]NO3, [4]PF6 and [4]BPh4 were investigated as catalytic precursors in the transfer hydrogenation reaction of ethyl levulinate to γ-valerolactone in isopropanol solution under microwave irradiation. [4]BPh4 was revealed to be the best catalytic precursor, affording γ-valerolactone in 62% yield under optimized experimental conditions.