| Popis: |
The complexes [(4′-Ph-terpy)Ru(H2O)3](OTf)2 and [(4′-Ph-terpy)Ir(OTf)3] have been evaluated as catalysts for the conversion of 2,5-hexanedione and 2,5-dimethylfuran to hydrodeoxygenated products in aqueous acidic medium at elevated temperature (150–225 °C) under hydrogen gas (5.5 MPa). These two substrates form part of a value chain leading from C6 sugars to 2,5-hexanediol, 2,5-dimethyltetrahydrofuran, and hexane, which can be generated by the homogeneously acting ruthenium catalyst in up to 69%, 80%, and 10% yield, respectively, while at T > 175 °C the iridium system decomposes to a highly active but heterogeneously acting coating in the reactor defeating the premise of a homogeneous catalyst system. The deactivation and decomposition pathway of both catalysts leads to the formation of a series of isostructural complexes [M(4′-Ph-terpy)2]n+ (M = Fe, Ni, Ru, Ir; n = 2, 3) characterized by ESI-MS and single crystal X-ray crystallography, in which the source of the Fe and Ni is the 316SS reactor body. |
