Experimental and Computational Studies on the Mechanism of N-Heterocycle C−H Activation by Rh(I)
| Autor: | Jonathan A. Ellman, Robert G. Bergman, Sean H. Wiedemann, Jared C. Lewis |
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| Rok vydání: | 2006 |
| Předmět: |
Models
Molecular chemistry.chemical_classification Reaction mechanism Molecular Structure Stereochemistry Alkene General Chemistry Crystallography X-Ray Biochemistry Oxidative addition Article Catalysis Coupling reaction Coordination complex Reaction coordinate Kinetics chemistry.chemical_compound Colloid and Surface Chemistry Reaction rate constant chemistry Quinazolines Thermodynamics Rhodium Carbene |
| Zdroj: | Journal of the American Chemical Society. 128:2452-2462 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja0576684 |
| Popis: | Evidence is presented for a proposed mechanism of C-H activation of 3-methyl-3,4-dihydroquinazoline (1) by (PCy(3))(2)RhCl. One intermediate (3), a coordination complex of 1 with (PCy(3))(2)RhCl, was identified along the path to the Rh-N-heterocyclic carbene product of this reaction (2). Isotopic labeling and reaction-rate studies were used to demonstrate that C-H activation takes place intramolecularly on the reaction coordinate between 3 and 2. Computational studies corroborate the proposed mechanism and suggest that the rate-limiting step is oxidative addition of the C-H bond to the metal center. The consequences of this mechanism for coupling reactions of N-heterocycles that occur via Rh-catalyzed C-H bond activation are discussed. |
| Databáze: | OpenAIRE |
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