Stereoselective Cycloaddition of 1,3-Cyclohexadiene on Si(100): A Simple Algorithm for Product Identification Based on Secondary Orbital Interactions
| Autor: | David E Meehan, Peter Ryan, John J. Boland, Lucile C. Teague |
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| Rok vydání: | 2011 |
| Předmět: |
chemical reaction
1 3-cyclohexadiene 1 3 cyclohexadiene DFT calculation 1 3-Cyclohexadiene Photochemistry Biochemistry Catalysis SIMPLE algorithm chemistry.chemical_compound Colloid and Surface Chemistry Surface chemical reactions Atomic orbital Molecule Reactivity (chemistry) Secondary interactions cycloaddition density functional theory Chemistry stereochemistry Frontier orbitals Stereoselectivity General Chemistry Molecular configuration dimer Molecular configurations Symmetry (physics) Cycloaddition Si(1 0 0) Chemical physics Stereo-selective Thermodynamics Orbital interaction Product identification Surface reactions |
| Zdroj: | Journal of the American Chemical Society. 133:14287-14292 |
| ISSN: | 1520-5126 0002-7863 |
| DOI: | 10.1021/ja111539b |
| Popis: | We consider the reaction of 1,3-cyclohexadiene (1,3-CHD) on Si(100) and show that the observed reactivity and stereoselectivity cannot be explained on the basis of thermodynamics. We postulate the existence of secondary orbital interactions (SOIs) and introduce a simple algorithm that examines all possible secondary interactions between the frontier orbitals of the molecule and the surface. We demonstrate using an orbital symmetry-based algorithm supported by DFT calculations that SOIs favor a particular molecular configuration, consistent with the experimental observations. The potential role of SOIs in controlling surface chemical reactions is discussed. © 2011 American Chemical Society. |
| Databáze: | OpenAIRE |
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