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  • Title: "Long-range" metal-ligand cooperation in H2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex.
    Author: Gunanathan C, Gnanaprakasam B, Iron MA, Shimon LJ, Milstein D.
    Journal: J Am Chem Soc; 2010 Oct 27; 132(42):14763-5. PubMed ID: 20925343.
    Abstract:
    The acridine-based pincer complex 1 exhibits an unprecedented mode of metal-ligand cooperation involving a "long-range" interaction between the distal acridine C9 position and the metal center. Reaction of 1 with H(2)/KOH results in H(2) splitting between the Ru center and C9 with concomitant dearomatization of the acridine moiety. DFT calculations show that this process involves the formation of a Ru dihydride intermediate bearing a bent acridine ligand in which C9 is in close proximity to a hydride ligand followed by through-space hydride transfer. Ammonia induces transfer of a hydride from the Ru center of 1 to C9 of the flexible acridine pincer ligand, forming an unusual dearomatized fac-acridine PNP complex.
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