[Ir2(μ-CH2)(CO)4 Me2PCH2P(Me2)2][CF3SO3]2, an Unprecedented Electrophilic Methylene Complex; H Addition to Prepare a Bridging Methyl Complex

Authors

  • Mark K. Reinking,

    1. Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA)
    Search for more papers by this author
  • Phillip E. Fanwick,

    1. Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA)
    Search for more papers by this author
  • Prof. Clifford P. Kubiak

    Corresponding author
    1. Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA)
    Current affiliation:
    1. Research Fellow of the Alfred P. Sloan Foundation, 1987–1989
    • Department of Chemistry, Purdue University, West Lafayette, IN 47907 (USA)
    Search for more papers by this author

  • This work was supported by the NSF (CHE-8707963). NSF support of the X-ray Diffraction Facility at Purdue and a generous loan of IrCl3 from Johnson-Matthey Inc. is gratefully acknowledged.

Abstract

original image

The μ-CH2 bridge of 1 is attacked nucleophilically and not—as usually the case—electrophilically. This dramatic difference between 1 and Herrmann carbene complexes might be due to the combination of dication character and four CO ligands, which reduces the electron density at the metal center available for the free p orbital of the CH2 ligand. Complex 1 is formed as shown in Equation (a) and reacts, for example, with the H donor HBsBumath image to give the methyl-bridged complex [Ir2(CO)2(μ-CH3)L2]X, X [DOUBLE BOND] CF3SO3.

Ancillary