A Bis(thiophosphinoyl)methanediide Palladium Complex: Coordinated Dianion or Nucleophilic Carbene Complex?


  • This work was supported by the CNRS and the Ecole Polytechnique.


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A question of identity: A palladium complex featuring a carbenic S,C,S-based pincer ligand is reported (see scheme). DFT calculations show that, unlike classical carbene complexes, coordination occurs through donation from a d orbital at the metal into the empty np orbital of the carbene fragment, with the nσ orbital essentially acting as a nonbonding orbital. The complex is shown to have nucleophilic character.