Proceedings of the 2015 2nd International Conference on Machinery, Materials Engineering, Chemical Engineering and Biotechnology

Mechanism of the Rhodium-Catalyzed Hydroformylation of 4-(1-phenylvinyl)pyridine: A Detailed Computational Investigation of the Regioselectivity and Chemoselectivity

Authors
Xiaoling Luo, Rong Chen
Corresponding Author
Xiaoling Luo
Available Online December 2015.
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/).

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Volume Title
Proceedings of the 2015 2nd International Conference on Machinery, Materials Engineering, Chemical Engineering and Biotechnology
Series
Advances in Engineering Research
Publication Date
December 2015
ISBN
978-94-6252-151-3
ISSN
2352-5401
DOI
10.2991/mmeceb-15.2016.36How to use a DOI?
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  -