Cationic Cobalt(II) Bisphosphine Hydroformylation Catalysis: In Situ Spectroscopic and Reaction Studies.

ABSTRACT: [HCo(CO)_x(bisphosphine)](BF₄), x = 1-3, is a highly active hydroformylation catalyst system, especially for internal branched alkenes. In situ infrared spectroscopy (IR), electron paramagnetic resonance (EPR), and nuclear magnetic resonance studies support the proposed catalyst formulation. IR studies reveal the formation of a dicationic Co(I) paramagnetic CO-bridged dimer, [Co₂(μ-CO)₂(CO)(bisphosphine)₂]²⁺, at lower temperatures formed from the reaction of two catalyst complexes via the elimination of H₂. DFT studies indicate a dimer structure with square-pyramidal and tetrahedral cobalt centers. This monomer-dimer equilibrium is analogous to that seen for HCo(CO)₄, reacting to eliminate

SUBMITTER: Hood DM 

PROVIDER: S-EPMC11864568 | biostudies-literature | 2023 Sep

REPOSITORIES: biostudies-literature