20012-50-4Relevant academic research and scientific papers
Diverse Mechanistic Pathways in Single-Site Heterogeneous Catalysis: Alcohol Conversions Mediated by a High-Valent Carbon-Supported Molybdenum-Dioxo Catalyst
Bedzyk, Michael J.,Das, Anusheela,Kratish, Yosi,Li, Jiaqi,Ma, Qing,Marks, Tobin J.
, p. 1247 - 1257 (2022/02/07)
With the increase in the importance of renewable resources, chemical research is shifting focus toward substituting petrochemicals with biomass-derived analogues and platform-molecule transformations such as alcohol processing. To these ends, in-depth mechanistic understanding is key to the rational design of catalytic systems with enhanced activity and selectivity. Here we discuss in detail the structure and reactivity of a single-site active carbon-supported molybdenum-dioxo catalyst (AC/MoO2) and the mechanism(s) by which it mediates alcohol dehydration. A range of tertiary, secondary, and primary alcohols as well as selected bio-based terpineols are investigated as substrates under mild reaction conditions. A combined experimental substituent effect/kinetic/kinetic isotope effect/EXAFS/DFT computational analysis indicates that (1) water assistance is a key element in the transition state; (2) the experimental kinetic isotopic effect and activation enthalpy are 2.5 and 24.4 kcal/mol, respectively, in good agreement with the DFT results; and (3) several computationally identified intermediates including Mo-oxo-hydroxy-alkoxide and cage-structured long-range water-coordinated Mo-dioxo species are supported by EXAFS. This structurally and mechanistically well-characterized single-site system not only effects efficient transformations but also provides insight into rational catalyst design for future biomass processes.
Rapid ether and alcohol C-O bond hydrogenolysis catalyzed by tandem high-valent metal triflate + supported Pd catalysts
Li, Zhi,Assary, Rajeev S.,Atesin, Abdurrahman C.,Curtiss, Larry A.,Marks, Tobin J.
supporting information, p. 104 - 107 (2014/01/23)
The thermodynamically leveraged conversion of ethers and alcohols to saturated hydrocarbons is achieved efficiently with low loadings of homogeneous M(OTf)n + heterogeneous Pd tandem catalysts (M = transition metal; OTf = triflate; n = 4). For example, Hf(OTf)4 mediates rapid endothermic ether a? alcohol and alcohol a? alkene equilibria, while Pd/C catalyzes the subsequent, exothermic alkene hydrogenation. The relative C-O cleavage rates scale as 3 > 2 > 1. The reaction scope extends to efficient conversion of biomass-derived ethers, such as THF derivatives, to the corresponding alkanes.
Efficient hydrodeoxygenation of ketones, phenols, and ethers promoted by platinum-heteropolyacid bifunctional catalysts
Itagaki, Shintaro,Matsuhashi, Naoki,Taniguchi, Kento,Yamaguchi, Kazuya,Mizuno, Noritaka
supporting information, p. 1086 - 1088 (2014/07/22)
A Cs2.5H0.5PW12O40-supported platinum catalyst (Pt/CsPW) could act as an efficient heterogeneous catalyst for hydrodeoxygenation of various types of oxygen-containing compounds such as ketones, phenols, and ethers. The observed catalysis was truly heterogeneous, and the retrieved Pt/CsPW could be reused.
Catalyst and method for the production of 1-olefins from 2-hydroxylkanes
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Page/Page column 5, (2008/06/13)
The present invention relates to a process for preparing 1-olefins from 2-hydroxyalkanes by catalytic elimination of water under nonisomerizing conditions and to a catalyst which is particularly well-suited for this process and formally comprises yttrium
