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Synthesis and Reactivity of Organometallic Intermediates Relevant to Cobalt-Catalyzed Hydroformylation
- Source :
- Angewandte Chemie (International ed. in English). 59(23)
- Publication Year :
- 2020
-
Abstract
- Intermediates relevant to cobalt-catalyzed alkene hydroformylation have been isolated and evaluated in fundamental organometallic transformations relevant to aldehyde formation. The 18-electron (R,R)-(iPr DuPhos)Co(CO)2 H has been structurally characterized, and it promotes exclusive hydrogenation of styrene in the presence of 50 bar of H2 /CO gas (1:1) at 100 °C. Deuterium-labeling studies established reversible 2,1-insertion of styrene into the Co-D bond of (R,R)-(iPr DuPhos)Co(CO)2 D. Whereas rapid β-hydrogen elimination from cobalt alkyls occurred under an N2 atmosphere, alkylation of (R,R)-(iPr DuPhos)Co(CO)2 Cl in the presence of CO enabled the interception of (R,R)-(iPr DuPhos)Co(CO)2 C(O)CH2 CH2 Ph, which upon hydrogenolysis under 4 atm H2 produced the corresponding aldehyde and cobalt hydride, demonstrating the feasibility of elementary steps in hydroformylation. Both the hydride and chloride derivatives, (X=H- , Cl- ), underwent exchange with free 13 CO. Under reduced pressure, (R,R)-(iPr DuPhos)Co(CO)2 Cl underwent CO dissociation to form (R,R)-(iPr DuPhos)Co(CO)Cl.
- Subjects :
- chemistry.chemical_classification
010405 organic chemistry
Alkene
Hydride
chemistry.chemical_element
General Medicine
General Chemistry
010402 general chemistry
01 natural sciences
Aldehyde
Medicinal chemistry
Catalysis
0104 chemical sciences
chemistry.chemical_compound
chemistry
Hydrogenolysis
DuPhos
Cobalt
Hydroformylation
Subjects
Details
- ISSN :
- 15213773
- Volume :
- 59
- Issue :
- 23
- Database :
- OpenAIRE
- Journal :
- Angewandte Chemie (International ed. in English)
- Accession number :
- edsair.doi.dedup.....64e6c88cfa9e7d9a35c6bb58d2a922b6