Computational and Experimental Investigation of Alkene Hydrogenation by a Pincer-Type [P2Si]Rh Complex: Alkane Release via Competitive σ-Bond Metathesis and Reductive Elimination
| Autor: | Kaitlyn E. DeMeulenaere, Michael J. Trenerry, Matthew T. Whited, Buck L. H. Taylor |
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| Rok vydání: | 2019 |
| Předmět: |
chemistry.chemical_classification
Alkane Silylation 010405 organic chemistry Trans effect Alkene Organic Chemistry 010402 general chemistry Metathesis 01 natural sciences Medicinal chemistry Reductive elimination 0104 chemical sciences Pincer movement Catalysis Inorganic Chemistry chemistry Physical and Theoretical Chemistry |
| Zdroj: | Organometallics. 38:1493-1501 |
| ISSN: | 1520-6041 0276-7333 |
| DOI: | 10.1021/acs.organomet.8b00922 |
| Popis: | A combined experimental and computational approach has been utilized to elucidate the mechanism of alkene hydrogenation by pincer-type [P2Si]Rh catalysts. Although [P2Si]Rh interacts with H2 to afford a dihydrogen σ-complex rather than a dihydride (seemingly an indication of facile reductive elimination from Rh(III)), alkane release occurs by competitive σ-bond metathesis (bimolecular) and reductive elimination (unimolecular) pathways. This unusual behavior is attributed to the strong trans influence of the silyl donor. |
| Databáze: | OpenAIRE |
| Externí odkaz: |
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