Synthesis and Reactivity of Organometallic Intermediates Relevant to Cobalt-Catalyzed Hydroformylation

Connor S. MacNeil, Lauren N. Mendelsohn, Hongyu Zhong, Tyler P. Pabst, Paul J. Chirik

Research output: Contribution to journalArticlepeer-review

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)-(iPrDuPhos)Co(CO)2H 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)-(iPrDuPhos)Co(CO)2D. Whereas rapid β-hydrogen elimination from cobalt alkyls occurred under an N2 atmosphere, alkylation of (R,R)-(iPrDuPhos)Co(CO)2Cl in the presence of CO enabled the interception of (R,R)-(iPrDuPhos)Co(CO)2C(O)CH2CH2Ph, 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 13CO. Under reduced pressure, (R,R)-(iPrDuPhos)Co(CO)2Cl underwent CO dissociation to form (R,R)-(iPrDuPhos)Co(CO)Cl.

Original languageEnglish (US)
Pages (from-to)8912-8916
Number of pages5
JournalAngewandte Chemie - International Edition
Volume59
Issue number23
DOIs
StatePublished - Jun 2 2020

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)

Keywords

  • P ligands
  • acyl complex
  • asymmetric catalysis
  • cobalt
  • structure elucidation

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