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)(PPh<sub>3</sub>)<sub>...
| Main Authors: | , , |
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| Format: | Citation Index Journal |
| Language: | English |
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2009
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| Online Access: | http://scholars.utp.edu.my/id/eprint/234/ http://scholars.utp.edu.my/id/eprint/234/1/paper.pdf |
| _version_ | 1848658937445875712 |
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| author | M.S., Shaharun H., Mukhtar B.K., Dutta |
| author_facet | M.S., Shaharun H., Mukhtar B.K., Dutta |
| author_sort | M.S., Shaharun |
| 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)(PPh<sub>3</sub>)<sub>3</sub>-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 6-31++G(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 H <sub>2</sub>-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%. © 2009 American Institute of Chemical Engineers.
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| first_indexed | 2025-11-13T07:22:28Z |
| format | Citation Index Journal |
| id | oai:scholars.utp.edu.my:234 |
| institution | Universiti Teknologi Petronas |
| institution_category | Local University |
| language | English |
| last_indexed | 2025-11-13T07:22:28Z |
| publishDate | 2009 |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | oai:scholars.utp.edu.my:2342017-01-19T08:25:49Z http://scholars.utp.edu.my/id/eprint/234/ Ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by Rh-based catalyst M.S., Shaharun H., Mukhtar B.K., Dutta TP Chemical technology 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)(PPh<sub>3</sub>)<sub>3</sub>-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 6-31++G(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 H <sub>2</sub>-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%. © 2009 American Institute of Chemical Engineers. 2009 Citation Index Journal NonPeerReviewed application/pdf en http://scholars.utp.edu.my/id/eprint/234/1/paper.pdf M.S., Shaharun and H., Mukhtar and B.K., Dutta (2009) Ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by Rh-based catalyst. [Citation Index Journal] http://www.scopus.com/inward/record.url?eid=2-s2.0-72149089349&partnerID=40&md5=a8b196c2afa18236ba346512711c55be 10.1002/aic.11936 10.1002/aic.11936 10.1002/aic.11936 |
| spellingShingle | TP Chemical technology M.S., Shaharun H., Mukhtar B.K., Dutta 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
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| title_full | Ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by Rh-based catalyst
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| title_fullStr | Ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by Rh-based catalyst
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| title_full_unstemmed | Ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by Rh-based catalyst
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| title_short | Ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by Rh-based catalyst
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| title_sort | ab initio energy calculations and macroscopic rate modeling of hydroformylation of higher alkenes by rh-based catalyst |
| topic | TP Chemical technology |
| url | http://scholars.utp.edu.my/id/eprint/234/ http://scholars.utp.edu.my/id/eprint/234/ http://scholars.utp.edu.my/id/eprint/234/ http://scholars.utp.edu.my/id/eprint/234/1/paper.pdf |