Hydrogen-Deuerium Exchange between TpRu(PMe3)(L)X (L = PMe3 and X = OH, OPh, Me, Ph, or NHPh; L = NCMe and X = Ph) and Deuterated Arene Solvents: Evidence for Metal-Mediated Processes

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This article discusses evidence for metal-mediated processes.

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Feng, Yuee; Lail, Marty; Foley, Nicholas A.; Gunnoe, T. Brent; Barakat, Khaldoon A.; Cundari, Thomas R., 1964- et al. May 24, 2006.

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This article discusses evidence for metal-mediated processes.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2006 American Chemical Society.

Abstract: At elevated temperatures (90-130 ËšC), complexes of the type TpRu(PMe3)2X (X = OH, OPh, Me, Ph, or NHPh; Tp = hydridotris(pyrazolyl)borate) undergo regioselective hydrogen-deuterium (H/D) exchange with deuterated arenes. For X = OH or NHPh, H/D exchange occurs at hydroxide and anilido ligands, respectively. For X = OH, OPh, Me, Ph, or NHPh, isotopic exchange occurs at the Tp 4-positions with only minimal deuterium incorporation at the Tp 3- or 5-positions or PMe3 ligands. For TpRu(PMe3)-(NCMe)Ph, the H/D exchange occurs at 60 ËšC at all three Tp positions and the phenyl ring. TpRu(PMe3)2-CI, TpRu(PMe3)2OTf(OTf = trifluoromethanesulfonate), and TpRu(PMe3)2SH do not initiate H/D exchange in C6D6 after extended periods of time at elevated temperatures. Mechanistic studies indicate that the likely pathway for the H/D exchange involves ligand dissociation (PMe3 or NCMe), Ru-mediated activation of an aromatic C-D bond, and deuteration of basic nondative ligand (hydroxide or anilido) or Tp positions via net D+ transfer.

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  • Journal of the American Chemical Society, 2006, Washington D.C.: American Chemical Society, pp. 7982-7994

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 128
  • Page Start: 7982
  • Page End: 7994
  • Pages: 13
  • Peer Reviewed: Yes

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Feng, Yuee; Lail, Marty; Foley, Nicholas A.; Gunnoe, T. Brent; Barakat, Khaldoon A.; Cundari, Thomas R., 1964- et al. Hydrogen-Deuerium Exchange between TpRu(PMe3)(L)X (L = PMe3 and X = OH, OPh, Me, Ph, or NHPh; L = NCMe and X = Ph) and Deuterated Arene Solvents: Evidence for Metal-Mediated Processes, article, May 24, 2006; [Washington, D.C.]. (https://digital.library.unt.edu/ark:/67531/metadc77139/: accessed June 7, 2023), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT College of Arts and Sciences.

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