Mechanism of the Rhodium-Catalyzed Hydroformylation of 4-(1-phenylvinyl)pyridine: A Detailed Computational Investigation of the Regioselectivity and Chemoselectivity
- DOI
- 10.2991/mmeceb-15.2016.36How to use a DOI?
- Keywords
- Hydroformylation, Hydrogenation, DFT, Chemoselectivity, Regioselectivity
- Abstract
The mechanism of 4-(1-phenylvinyl)pyridine hydroformylation with HRh(CO)(PH3)3 as active catalyst has been proposed and discussed by B3LYP. Also, the regioselectivity and chemoselectivity are investigated by calculations and excellent agreement with the existing experimental results is displayed. It is found that the characteristic catalytic cycle is similar to that for olefin hydroformylation: (a) 4-(1-phenylvinyl)pyridine coordination and insertion, (b) CO coordination and insertion, and (c) H2 oxidative addition as well as aldehyde elimination. The rate-limiting and regioselectivity- determining step are H2 oxidative addition which determines the linear aldehyde product energetically. The competitive hydrogenation is along with (a) 4-(1-phenylvinyl)pyridine coordination and insertion, (b) H2 oxidative addition followed by hydrogenation product elimination Interestingly, CO coordination is found to be an exothermic ( H<0) but endergonic ( G>0) process, while the corresponding H2 process is endergonic and endothermic( H>0), H2 is not competitive with CO from the viewpoint of thermodynamics. But hydrogenation is computed to be more favored than hydroformylation actually, so it can be conclude that the chemoselectivity is controlled by kinetics, not thermodynamics.
- Copyright
- © 2016, the Authors. Published by Atlantis Press.
- Open Access
- This is an open access article distributed under the CC BY-NC license (http://creativecommons.org/licenses/by-nc/4.0/).
Cite this article
TY - CONF AU - Xiaoling Luo AU - Rong Chen PY - 2015/12 DA - 2015/12 TI - Mechanism of the Rhodium-Catalyzed Hydroformylation of 4-(1-phenylvinyl)pyridine: A Detailed Computational Investigation of the Regioselectivity and Chemoselectivity BT - Proceedings of the 2015 2nd International Conference on Machinery, Materials Engineering, Chemical Engineering and Biotechnology PB - Atlantis Press SP - 172 EP - 177 SN - 2352-5401 UR - https://doi.org/10.2991/mmeceb-15.2016.36 DO - 10.2991/mmeceb-15.2016.36 ID - Luo2015/12 ER -