Ab Initio Energy Calculations and Macroscopic Rate Modeling of Hydroformylation of Higher Alkenes by Rh-Based Catalyst
Ab initio quantum chemical computations have been done to determine the energetics and reaction pathways of hydroformylation of higher alkenes using a rhodium complex homogeneous catalyst. Calculation of fragments of the potential energy surfaces of the HRh(CO)(PPh3)3-catalyzed hydroformylation o...
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| Format: | Citation Index Journal |
| Language: | English English |
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Wiley Subscription Services Inc.
2009
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| Online Access: | http://scholars.utp.edu.my/id/eprint/2486/ http://scholars.utp.edu.my/id/eprint/2486/1/AIChE_J_Proof_July_12.pdf http://scholars.utp.edu.my/id/eprint/2486/2/AIChE_J_Proof_July_12.pdf |
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| author | Shaharun, Maizatul Shima B.K., Dutta H., Mukhtar |
| author_facet | Shaharun, Maizatul Shima B.K., Dutta H., Mukhtar |
| author_sort | Shaharun, Maizatul Shima |
| building | UTP Institutional Repository |
| collection | Online Access |
| description | Ab initio quantum chemical computations have been done to determine the energetics
and reaction pathways of hydroformylation of higher alkenes using a rhodium
complex homogeneous catalyst. Calculation of fragments of the potential energy surfaces
of the HRh(CO)(PPh3)3-catalyzed hydroformylation of 1-decene, 1-dodecene, and
styrene were performed by the restricted Hartree-Fock method at the second-order
MØller-Plesset (MP2) level of perturbation theory and basis set of 6-31þþG(d,p).
Geometrically optimized structures of the intermediates and transition states were
identified. Three generalized rate models were developed on the basis of above
reaction path analysis as well as experimental findings reported in the literature. The
kinetic and equilibrium parameters of the models were estimated by nonlinear least
square regression of available literature data. The model based on H2-oxidative addition
fitted the data best; it predicts the conversion of all the alkenes quite satisfactorily
with an average deviation of 7.6% and a maximum deviation of 13%. |
| first_indexed | 2025-11-13T07:27:34Z |
| format | Citation Index Journal |
| id | oai:scholars.utp.edu.my:2486 |
| institution | Universiti Teknologi Petronas |
| institution_category | Local University |
| language | English English |
| last_indexed | 2025-11-13T07:27:34Z |
| publishDate | 2009 |
| publisher | Wiley Subscription Services Inc. |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | oai:scholars.utp.edu.my:24862017-01-19T08:25:08Z http://scholars.utp.edu.my/id/eprint/2486/ Ab Initio Energy Calculations and Macroscopic Rate Modeling of Hydroformylation of Higher Alkenes by Rh-Based Catalyst Shaharun, Maizatul Shima B.K., Dutta H., Mukhtar QD Chemistry Ab initio quantum chemical computations have been done to determine the energetics and reaction pathways of hydroformylation of higher alkenes using a rhodium complex homogeneous catalyst. Calculation of fragments of the potential energy surfaces of the HRh(CO)(PPh3)3-catalyzed hydroformylation of 1-decene, 1-dodecene, and styrene were performed by the restricted Hartree-Fock method at the second-order MØller-Plesset (MP2) level of perturbation theory and basis set of 6-31þþG(d,p). Geometrically optimized structures of the intermediates and transition states were identified. Three generalized rate models were developed on the basis of above reaction path analysis as well as experimental findings reported in the literature. The kinetic and equilibrium parameters of the models were estimated by nonlinear least square regression of available literature data. The model based on H2-oxidative addition fitted the data best; it predicts the conversion of all the alkenes quite satisfactorily with an average deviation of 7.6% and a maximum deviation of 13%. Wiley Subscription Services Inc. 2009-12 Citation Index Journal NonPeerReviewed application/pdf en http://scholars.utp.edu.my/id/eprint/2486/1/AIChE_J_Proof_July_12.pdf application/pdf en http://scholars.utp.edu.my/id/eprint/2486/2/AIChE_J_Proof_July_12.pdf Shaharun, Maizatul Shima and B.K., Dutta and H., Mukhtar (2009) Ab Initio Energy Calculations and Macroscopic Rate Modeling of Hydroformylation of Higher Alkenes by Rh-Based Catalyst. [Citation Index Journal] http://www.interscience.wiley.com 10.1002/aic.11936 10.1002/aic.11936 10.1002/aic.11936 |
| spellingShingle | QD Chemistry Shaharun, Maizatul Shima B.K., Dutta H., Mukhtar Ab Initio Energy Calculations and Macroscopic Rate Modeling of Hydroformylation of Higher Alkenes by Rh-Based Catalyst |
| title | Ab Initio Energy Calculations and Macroscopic
Rate Modeling of Hydroformylation of Higher
Alkenes by Rh-Based Catalyst |
| title_full | Ab Initio Energy Calculations and Macroscopic
Rate Modeling of Hydroformylation of Higher
Alkenes by Rh-Based Catalyst |
| title_fullStr | Ab Initio Energy Calculations and Macroscopic
Rate Modeling of Hydroformylation of Higher
Alkenes by Rh-Based Catalyst |
| title_full_unstemmed | Ab Initio Energy Calculations and Macroscopic
Rate Modeling of Hydroformylation of Higher
Alkenes by Rh-Based Catalyst |
| title_short | Ab Initio Energy Calculations and Macroscopic
Rate Modeling of Hydroformylation of Higher
Alkenes by Rh-Based Catalyst |
| title_sort | ab initio energy calculations and macroscopic
rate modeling of hydroformylation of higher
alkenes by rh-based catalyst |
| topic | QD Chemistry |
| url | http://scholars.utp.edu.my/id/eprint/2486/ http://scholars.utp.edu.my/id/eprint/2486/ http://scholars.utp.edu.my/id/eprint/2486/ http://scholars.utp.edu.my/id/eprint/2486/1/AIChE_J_Proof_July_12.pdf http://scholars.utp.edu.my/id/eprint/2486/2/AIChE_J_Proof_July_12.pdf |