Heterolytic Outer-Sphere Cleavage of H2 for the Reduction of N2 in the Coordination Sphere of Transition Metals—A DFT Study

Authors

  • Dr. Markus Hölscher,

    Corresponding author
    1. Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany)
    • Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany)
    Search for more papers by this author
  • Prof. Dr. Walter Leitner

    Corresponding author
    1. Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany)
    • Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 1, 52074 Aachen (Germany)
    Search for more papers by this author

  • We are grateful for the generous allocation of computer time by the Rechen- und Kommunikationszentrum of RWTH Aachen University. Assistance with the B2PLY-D computations by Dr. A. Uhe is gratefully acknowledged.

Abstract

original image

Cleaved by frustration, an H2 molecule inserts into the void between the components of the frustrated Lewis pair 1, which consists of a dicationic ruthenium pincer complex as the Lewis acid and (tBu)3P as the Lewis base. The end-on-coordinated N2 in 1 accepts the hydride, and this is the initial step, which could, in principle, lead to the complete reduction of N2 to NH3.

Ancillary