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Synthesis and Reactivity of Organometallic Intermediates Relevant to Cobalt-Catalyzed Hydroformylation.
MacNeil, Connor S; Mendelsohn, Lauren N; Zhong, Hongyu; Pabst, Tyler P; Chirik, Paul J.
Afiliación
  • MacNeil CS; Department of Chemistry, Princeton University, Frick Laboratory 292, Princeton, NJ, 08544, USA.
  • Mendelsohn LN; Department of Chemistry, Princeton University, Frick Laboratory 292, Princeton, NJ, 08544, USA.
  • Zhong H; Department of Chemistry, Princeton University, Frick Laboratory 292, Princeton, NJ, 08544, USA.
  • Pabst TP; Department of Chemistry, Princeton University, Frick Laboratory 292, Princeton, NJ, 08544, USA.
  • Chirik PJ; Department of Chemistry, Princeton University, Frick Laboratory 292, Princeton, NJ, 08544, USA.
Angew Chem Int Ed Engl ; 59(23): 8912-8916, 2020 Jun 02.
Article en En | MEDLINE | ID: mdl-32182395
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 ß-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.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2020 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Alemania
Texto completo
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XML
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Idioma: En Revista: Angew Chem Int Ed Engl Año: 2020 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Alemania