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Open Access Publications from the University of California

Reactivity of a series of isostructural cobalt pincer complexes with CO2, CO, and H+

  • Author(s): Shaffer, DW
  • Johnson, SI
  • Rheingold, AL
  • Ziller, JW
  • Goddard, WA
  • Nielsen, RJ
  • Yang, JY
  • et al.

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© 2014 American Chemical Society. The preparation and characterization of a series of isostructural cobalt complexes [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2(Py = pyridine, E = CH2, NH, O, and X = BF4(1a-c)) and the corresponding one-electron reduced analogues [Co(t-Bu)2PEPyEP(t-Bu)2(CH3CN)2][BF4]2(2a-c) are reported. The reactivity of the reduced cobalt complexes with CO2, CO, and H+to generate intermediates in a CO2to CO and H2O reduction cycle are described. The reduction of 1a-c and subsequent reactivity with CO2was investigated by cyclic voltammetry, and for 1a also by infrared spectroelectrochemistry. The corresponding CO complexes of (2a-c) were prepared, and the Co-CO bond strengths were characterized by IR spectroscopy. Quantum mechanical methods (B3LYP-d3 with solvation) were used to characterize the competitive reactivity of the reduced cobalt centers with H+versus CO2. By investigating a series of isostructural complexes, correlations in reactivity with ligand electron withdrawing effects are made.

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