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首页> 外文期刊>Chemistry: A European journal >An Operando FTIR Spectroscopic and Kinetic Study of Carbon Monoxide Pressure Influence on Rhodium-Catalyzed Olefin Hydroformylation
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An Operando FTIR Spectroscopic and Kinetic Study of Carbon Monoxide Pressure Influence on Rhodium-Catalyzed Olefin Hydroformylation

机译：一氧化碳压力对铑催化的烯烃加氢甲酰化反应的影响FTIR光谱和动力学研究

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摘要

The influence of carbon monoxide concentration on the kinetics of the hydroformylation of 3,3-dimethyl-1-butene with a phosphite-modified rhodium catalyst has been studied for the pressure range p(CO)=0.20–3.83 MPa. Highly resolved time-dependent concentration profiles of the organometallic intermediates were derived from IR spectroscopic data collected in situ for the entire olefin-conversion range. The dynamics of the catalyst and organic components are described by enzyme-type kinetics with competitive and uncompetitive inhibition reactions involving carbon monoxide taken into account. Saturation of the alkyl–rhodium intermediates with carbon monoxide as a cosubstrate occurs between 1.5 and 2 MPa of carbon monoxide pressure, which brings about a convergence of aldehyde regioselectivity. Hydrogenolysis of the acyl intermediate is fast at 308C and low pressure of p(CO)=0.2 MPa, but is of minus first order with respect to the solution concentration of carbon monoxide. Resting 18-electron hydrido and acyl complexes that correspond to early and late rate-determining states, respectively, coexist as long as the conversion of the substrate is not complete.
机译：在压力范围p（CO）= 0.20-3.83 MPa的条件下，研究了一氧化碳浓度对亚磷酸酯修饰的铑催化剂对3,3-二甲基-1-丁烯加氢甲酰化反应动力学的影响。有机金属中间体的高度分辨的时间依赖性浓度分布图是从就整个烯烃转化范围而言就地收集的红外光谱数据得出的。催化剂和有机组分的动力学由酶型动力学描述，其中考虑了涉及一氧化碳的竞争性和非竞争性抑制反应。烷基铑中间体与一氧化碳作为共底物的饱和发生在一氧化碳压力介于1.5和2 MPa之间，这导致醛区域选择性趋于一致。酰基中间体的氢解在308°C时快速，p（CO）= 0.2 MPa的低压很短，但是相对于一氧化碳的溶液浓度来说却是负一阶。只要底物的转化不完全，分别对应于早期和晚期速率确定状态的静止的18电子氢化物和酰基络合物并存。

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