Hydrodeoxygenation of 2,5-Hexanedione and 2,5-Dimethylfuran by Water-, Air-, and Acid-Stable Homogeneous Ruthenium and Iridium Catalysts

详细信息    查看全文

• 作者：Ryan J. Sullivan ; Elnaz Latifi ; Benjamin K.-M. Chung ; Dmitriy V. Soldatov ; Marcel Schlaf
• 刊名：ACS Catalysis
• 出版年：2014
• 出版时间：November 7, 2014
• 年：2014
• 卷：4
• 期：11
• 页码：4116-4128
• 全文大小：573K
• ISSN：2155-5435

文摘

The complexes [(4鈥?Ph-terpy)Ru(H₂O)₃](OTf)₂ and [(4鈥?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鈥?25 掳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 掳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鈥?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.

Keywords:

homogeneous catalysis; aqueous media; hydrogenation; hydrodeoxygenation; biomass conversion; catalyst decomposition