"Long-range" metel-ligand cooperation in h2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex

Chidambaram Gunanathan, Boopathy Gnanaprakasam, Mark A. Iron, Linda J W Shimon, David Milstein

Research output: Contribution to journalArticle

95 Citations (Scopus)

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 H2 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.

Original languageEnglish
Pages (from-to)14763-14765
Number of pages3
JournalJournal of the American Chemical Society
Volume132
Issue number42
DOIs
Publication statusPublished - Oct 27 2010

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Acridines
Ruthenium
Ammonia
Hydrides
Chemical activation
Ligands
Bearings (structural)
Metals
Discrete Fourier transforms

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

"Long-range" metel-ligand cooperation in h2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex. / Gunanathan, Chidambaram; Gnanaprakasam, Boopathy; Iron, Mark A.; Shimon, Linda J W; Milstein, David.

In: Journal of the American Chemical Society, Vol. 132, No. 42, 27.10.2010, p. 14763-14765.

Research output: Contribution to journalArticle

Gunanathan, Chidambaram ; Gnanaprakasam, Boopathy ; Iron, Mark A. ; Shimon, Linda J W ; Milstein, David. / "Long-range" metel-ligand cooperation in h2 activation and ammonia-promoted hydride transfer with a ruthenium-acridine pincer complex. In: Journal of the American Chemical Society. 2010 ; Vol. 132, No. 42. pp. 14763-14765.
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