1998 Fiscal Year Final Research Report Summary
Simulation of Selective Chemical Reactions and Theoretical Elucidation of their Mechanisms.
| Project/Area Number |
09650901
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| Research Category |
Grant-in-Aid for Scientific Research (C)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Research Field |
工業物理化学
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| Research Institution | Nagoya University |
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Principal Investigator |
KOGA Nobuaki Graduate School of Human Informatics, Professor, 大学院・人間情報学研究科, 教授 (80186650)
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| Project Period (FY) |
1997 – 1998
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| Keywords | MO-then-MM method / IMOMM method / selective reactions / transition metal complex catalyst / asymmetric catalyst / 不斉触媒 |
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| Research Abstract |
In order to analyze the mechanism of selective reactions catalyzed by transition metal complexes and obtain useful information on devising catalysts, we have performed theoretical calculations of several model chemical reactions using the methods combining quantum mechanical and molecular mechanics calculations. The model reactions are 1) altering copolymerization of propylene with carbon monoxide catalyzed by Pd complexes with BINAPHOS ligand, 2) isotactic propylene polymerization catalyzed by a Sm complex, and 3) hydroformylation catalyzed by Rh-BINAPHOS catalysts. As to the first reaction, we first studied with the DFT method the propylene insertion into the PdC bond of Pd(COCH_3)(PH_3)(P(OH)_3)+ to clarify the reaction mechanism and with the MO-then-MM method the retio- and stereoselectivity due to the BINAPHOS ligand. We found that the steric effect due to the BINAPHOS ligand actually controls the stereo- and regioselectivity. In the MO-then-MM calculations of propylene insertion into the Sm-C bond of substituted samarocene alkyl complex, we have found that the propylene insertion would be isotactic, and different from the reaction catalyzed by the d block transition metal complexes, secondary insertion is more favorable. The different control mechanism is operational.
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Research Products
(4 results)
