A pentacoordinated norbornenyl-acyl-rhodium(iii ) complex as a likely intermediate in the catalytic hydroacylation of norbornadiene
| Autor: | María A. Garralda, José M. Seco, Antonio Rodríguez-Diéguez, Claudio Mendicute-Fierro, Lourdes Ibarlucea, Miguel A. Huertos, N. Almenara |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
chemistry.chemical_classification
Ketone 010405 organic chemistry Stereochemistry Norbornadiene Hydroacylation chemistry.chemical_element 010402 general chemistry Ring (chemistry) 01 natural sciences Medicinal chemistry Aldehyde 0104 chemical sciences Rhodium Catalysis Inorganic Chemistry chemistry.chemical_compound chemistry Isomerization |
| Zdroj: | Dalton Transactions. 45:18502-18509 |
| ISSN: | 1477-9234 1477-9226 |
| Popis: | [RhCl(NCO)(nbyl)(PR3)] (nbyl = σ-norbornenyl; NCO = quinoline-8-acyl; R = p-F-C6H4) (1) has been synthesized by the reaction of [Rh(nbd)Cl]2 (nbd = norbornadiene) with 2 equivalents of NCHO (quinoline-8-carbaldehyde) and 2 equivalents of PR3. Compound 1 has been fully characterized in solution and also in the solid state by X-ray diffraction. Compound 1 shows low stability in solution and undergoes slow ring closure isomerization to [RhCl(NCO)(ntyl)(PR3)] (ntyl = σ-nortricyclyl) (2) after 12 hours. Reaction of 1 with an extra equivalent of aldehyde (NCHO) and PR3 led to the formation of [RhCl(H)(NCO)(PR3)2] (3) and an equivalent of ketone, which is a hydroacylation product. The catalytic activity of 3 in the hydroacylation of nbd with NCHO is reported as well as the catalytic activity of compound 1. Compounds 1 and 3 are proposed as intermediate species in the catalytic hydroacylation of norbornadiene with NCHO. |
| Databáze: | OpenAIRE |
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