Description

Attempts to prepare low-valent molybdenum complexes that feature a pentadentate 2,6-bis(imino)pyridine (or pyridine diimine, PDI) chelate allowed for the isolation of two different products. Refluxing Mo(CO)6 with the pyridine-substituted PDI ligand, PyEtPDI, resulted in carbonyl ligand substitution and formation of

Attempts to prepare low-valent molybdenum complexes that feature a pentadentate 2,6-bis(imino)pyridine (or pyridine diimine, PDI) chelate allowed for the isolation of two different products. Refluxing Mo(CO)6 with the pyridine-substituted PDI ligand, PyEtPDI, resulted in carbonyl ligand substitution and formation of the respective bis(ligand) compound (PyEtPDI)2Mo (1). This complex was investigated by single-crystal X-ray diffraction, and density functional theory calculations indicated that 1 possesses a Mo(0) center that back-bonds into the π*-orbitals of the unreduced PDI ligands. Heating an equimolar solution of Mo(CO)[subscript 6] and the phosphine-substituted PDI ligand, Ph2PPrPDI, to 120 °C allowed for the preparation of (Ph2PPrPDI)Mo(CO) (2), which is supported by a κ5-N,N,N,P,P-Ph2PPrPDI chelate. Notably, 1 and 2 have been found to catalyze the hydrosilylation of benzaldehyde at 90 °C, and the optimization of 2-catalyzed aldehyde hydrosilylation at this temperature afforded turnover frequencies of up to 330 h–1. Considering additional experimental observations, the potential mechanism of 2-mediated carbonyl hydrosilylation is discussed.

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Title
  • Preparation and Hydrosilylation Activity of a Molybdenum Carbonyl Complex That Features a Pentadentate Bis(imino)pyridine Ligand
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Date Created
2014-09-01
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    Identifier
    • Digital object identifier: 10.1021/ic501465v
    • Identifier Type
      International standard serial number
      Identifier Value
      0020-1669
    • Identifier Type
      International standard serial number
      Identifier Value
      1520-510X

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    Pal, Raja, Groy, Thomas L., Bowman, Amanda C., & Trovitch, Ryan J. (2014). Preparation and Hydrosilylation Activity of a Molybdenum Carbonyl Complex That Features a Pentadentate Bis(imino)pyridine Ligand. INORGANIC CHEMISTRY, 53(17), 9357-9365. http://dx.doi.org/10.1021/ic501465v

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