Volume 135, Issue 21 e202302777
Forschungsartikel

Fast Isomerization Before Isomerization-Hydroformylation: Probing the Neglected Period with A Novel Microfluidic Device

Dr. Fanfu Guan

Dr. Fanfu Guan

Department of Chemical Process R&D, Lianyungang Institute of Research, Jiangsu Hengrui Pharmaceuticals Co., Ltd., 7 Kunlunshan Road, Lianyungang, 222000 China

These authors contributed equally to this work.

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Yu Qian

Yu Qian

Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Road, Shenzhen, 518055 China

These authors contributed equally to this work.

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Peiqi Zhang

Peiqi Zhang

Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Road, Shenzhen, 518055 China

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Dr. Runtong Zhang

Dr. Runtong Zhang

Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Road, Shenzhen, 518055 China

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Prof. Xumu Zhang

Corresponding Author

Prof. Xumu Zhang

Guangdong Provincial Key Laboratory of Catalysis, Department of Chemistry, Southern University of Science and Technology, 1088 Xueyuan Road, Shenzhen, 518055 China

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Dr. Jialin Wen

Corresponding Author

Dr. Jialin Wen

Department of Chemical Process R&D, Lianyungang Institute of Research, Jiangsu Hengrui Pharmaceuticals Co., Ltd., 7 Kunlunshan Road, Lianyungang, 222000 China

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First published: 20 March 2023
Citations: 2

Abstract

By combining the concept of flash chemistry and radial synthesis, a novel microreactor (Flashstop reactor) was designed to study isomerization process of hydroformylation by a Rh/tetraphosphite catalyst in a time scale of seconds. It was found that in the initial 313 seconds, 60–99 % of 1-octene was isomerized to 2- and 3-octenes before the formation of aldehydes. Within this period, two different types of isomerization reactions were observed. It was proposed that a monohydride complex without CO ligand accounts for the ultrafast isomerization in the initial 30 seconds. The isomerization rate with such monohydride species was calculated much faster than that with the well-known H(CO)Rh(P−P) species. Both experimental and DFT computational studies were carried out to support this assumption. Fast transformations early on in catalytic cycles have been rarely studied due to the lack of proper tools. We believe that the Flashstop reactor is a powerful tool for analysis of kinetics in gas-liquid biphasic reactions within a time scale of seconds to minutes.

Conflict of interest

The authors declare no conflict of interest.

Data Availability Statement

The data that support the findings of this study are available in the Supporting Information of this article.

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