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Multi-nuclear, high-pressure, operando FlowNMR spectroscopic study of Rh/PPh3 – catalysed hydroformylation of 1-hexene
Faraday Discussions ( IF 3.3 ) Pub Date : 2020-3-26 , DOI: 10.1039/c9fd00145j Alejandro Bara-Estaún 1, 2, 3, 4, 5 , Catherine L. Lyall 1, 2, 3, 4, 5 , John P. Lowe 1, 2, 3, 4, 5 , Paul G. Pringle 4, 6, 7, 8 , Paul C. J. Kamer 9, 10, 11 , Robert Franke 11, 12, 13 , Ulrich Hintermair 1, 2, 3, 4, 5
Faraday Discussions ( IF 3.3 ) Pub Date : 2020-3-26 , DOI: 10.1039/c9fd00145j Alejandro Bara-Estaún 1, 2, 3, 4, 5 , Catherine L. Lyall 1, 2, 3, 4, 5 , John P. Lowe 1, 2, 3, 4, 5 , Paul G. Pringle 4, 6, 7, 8 , Paul C. J. Kamer 9, 10, 11 , Robert Franke 11, 12, 13 , Ulrich Hintermair 1, 2, 3, 4, 5
Affiliation
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The hydroformylation of 1-hexene with 12 bar of 1 : 1 H2/CO in the presence of the catalytic system [Rh(acac)(CO)2]/PPh3 was successfully studied by real-time multinuclear high-resolution FlowNMR spectroscopy at 50 °C. Quantitative reaction progress curves that yield rates as well as chemo- and regioselectivities have been obtained with varying P/Rh loadings. Dissolved H2 can be monitored in solution to ensure true operando conditions without gas limitation. 31P{1H} and selective excitation 1H pulse sequences have been periodically interleaved with 1H FlowNMR measurements to detect Rh–phosphine intermediates during the catalysis. Stopped-flow experiments in combination with diffusion measurements and 2D heteronuclear correlation experiments showed the known tris-phosphine complex [RhH(CO)(PPh3)3] to generate rapidly exchanging isomers of the bis-phosphine complex [Rh(CO)2(PPh3)2] under CO pressure that directly enter the catalytic cycle. A new mono-phosphine acyl complex has been identified as an in-cycle reaction intermediate.
中文翻译：
Rh / PPh3催化的1-己烯加氢甲酰化反应的多核高压操作流式NMR光谱研究
通过实时多核高分辨率流动NMR光谱研究了催化体系[Rh（acac）（CO）2 ] / PPh 3存在下1-己烯与12 bar 1：1 H 2 / CO的加氢甲酰化反应在50°C下。在不同的P / Rh载量下，获得了产率，化学选择性和区域选择性的定量反应进程曲线。可以在溶液中监测溶解的H 2，以确保没有气体限制的真实操作条件。31 P { 1 H}和选择性激励1 H脉冲序列已与1H FlowNMR测量可检测催化过程中的Rh-膦中间体。结合扩散测量和2D异核相关实验的停止流实验表明，已知的tris-膦配合物[RhH（CO）（PPh 3）3 ]生成了双膦配合物[Rh（CO）2（ PPh 3）2 ]在CO压力下直接进入催化循环。一种新的单膦酰基复合物已被确认为循环反应中间体。
更新日期：2020-03-26
中文翻译：
Rh / PPh3催化的1-己烯加氢甲酰化反应的多核高压操作流式NMR光谱研究
通过实时多核高分辨率流动NMR光谱研究了催化体系[Rh（acac）（CO）2 ] / PPh 3存在下1-己烯与12 bar 1：1 H 2 / CO的加氢甲酰化反应在50°C下。在不同的P / Rh载量下，获得了产率，化学选择性和区域选择性的定量反应进程曲线。可以在溶液中监测溶解的H 2，以确保没有气体限制的真实操作条件。31 P { 1 H}和选择性激励1 H脉冲序列已与1H FlowNMR测量可检测催化过程中的Rh-膦中间体。结合扩散测量和2D异核相关实验的停止流实验表明，已知的tris-膦配合物[RhH（CO）（PPh 3）3 ]生成了双膦配合物[Rh（CO）2（ PPh 3）2 ]在CO压力下直接进入催化循环。一种新的单膦酰基复合物已被确认为循环反应中间体。
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