Study on regioselectivity in cobalt catalyzed hydroformylation of α-hexene

HE Xiao-fei; GUO Jing; XIA Hong-qiang; ZHAO Tian-sheng

doi:10.1016/S1872-5813(21)60131-7

Volume 50 Issue 1

Jan. 2022

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Article Navigation > Journal of Fuel Chemistry and Technology > 2022 > 50(1): 72-79

HE Xiao-fei, GUO Jing, XIA Hong-qiang, ZHAO Tian-sheng. Study on regioselectivity in cobalt catalyzed hydroformylation of α-hexene[J]. Journal of Fuel Chemistry and Technology, 2022, 50(1): 72-79. doi: 10.1016/S1872-5813(21)60131-7

Citation:

HE Xiao-fei, GUO Jing, XIA Hong-qiang, ZHAO Tian-sheng. Study on regioselectivity in cobalt catalyzed hydroformylation of α-hexene[J]. Journal of Fuel Chemistry and Technology, 2022, 50(1): 72-79. doi: 10.1016/S1872-5813(21)60131-7

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Study on regioselectivity in cobalt catalyzed hydroformylation of α-hexene

doi: 10.1016/S1872-5813(21)60131-7

State Key Laboratory of High-efficiency Utilization of Coal and Green Chemical Engineering, College of Chemistry & Chemical Engineering, Ningxia University, Yinchuan 750021, China

Funds: The project was supported by the East-West Cooperation Project, Key R & D Plan of Ningxia (2017BY063)

Received Date: 2021-05-07
Rev Recd Date: 2021-06-20

Available Online: 2021-07-19

Publish Date: 2022-01-25

Abstract

Abstract

Regioselective effects of electron and steric hindrance of catalytically active intermediate HCo(CO)₂L coordinated by phosphine ligands on α-hexene hydroformylation were studied based on density functional theory. Phosphine ligands have strong electron-attracting capacity that raises the stability of HCo(CO)₂L. PPh₃ with large steric hindrance suppresses the coordination of α-hexene with HCo(CO)₂L as well as the secondary reaction of the C=C with the Co–H via the branched chain pathway. The energy barrier for the transition state containing linear chain alkyl Co intermediate is lower about 2.73 kcal/mol than that for the transition state with branched chain alkyl Co intermediate, indicating that linear chain pathway is dominant in the addition reaction. Both the electron and steric hindrance effects of phosphine ligands determines the pathway of addition reaction between the C=C of α-hexene and the Co–H. The linear chain addition is preferable that mainly produces linear chain aldehydes.
- cobalt,
- phosphine ligand,
- α-hexene,
- hydroformylation,
- regioselectivity,
- DFT

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References(28)

References

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