Final Technical Report "Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation" Grant number : DE-FG02-86ER13615

[摘要] Title: Catalytic Hydrogenation of Carbon Monoxide and Olefin Oxidation Grant No. DE-FG02-86ER13615 PI: Wayland, B. B. ([e-mail]) Abstract Development of new mechanistic strategies and catalyst materials for activation of CO, H2, CH4, C2H4, O2, and related substrates relevant to the conversion of carbon monoxide, alkanes, and alkenes to organic oxygenates are central objectives encompassed by this program. Design and synthesis of metal complexes that manifest reactivity patterns associated with potential pathways for the hydrogenation of carbon monoxide through metallo-formyl (M-CHO), dimetal ketone (M-C(O)-M), and dimetal dionyl (M-C(O)-C(O)-M) species is one major focus. Hydrocarbon oxidation using molecular oxygen is a central goal for methane activation and functionalization as well as regioselective oxidation of olefins. Discovery of new reactivity patterns and control of selectivity are pursued through designing new metal complexes and adjusting reaction conditions. Variation of reaction media promotes distinct reaction pathways that control both reaction rates and selectivities. Dimetalloradical diporphyrin complexes preorganize transition states for substrate reactions that involve two metal centers and manifest large rate increases over mono-metalloradical reactions of hydrogen, methane, and other small molecule substrates. Another broad goal and recurring theme of this program is to contribute to the thermodynamic database for a wide scope of organo-metal transformations in a range of reaction media. One of the most complete descriptions of equilibrium thermodynamics for organometallic reactions in water and methanol is emerging from the study of rhodium porphyrin substrate reactions in aqueous and alcoholic media. Water soluble group nine metalloporphyrins manifest remarkably versatile substrate reactivity in aqueous and alcoholic media which includes producing rhodium formyl (Rh-CHO) and hydroxy methyl (Rh-CH2OH) species. Exploratory directions for this program include expending new strategies for anti-Markovnikov addition of water, alcohols, and amines with olefins, developing catalytic reactions of CO to give formamides and formic esters, and evaluating the potential for coupling reactions of CO to produce organic building blocks.

[发布日期] 2009-08-31

[学科分类] 燃料技术

[关键词] Carbon Monoxide;hydrogenation;olefin oxidation;CO reduction;CO coupling.