Variable Pathways for Oxygen Atom Insertion into Metal-Carbon Bonds: The Case of Cp*W(O)₂(CH₂SiMe₃)

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Article discussing variable pathways for oxygen atom insertion into metal-carbon bonds and the case of Cp*W(O)2(CH2SiMe3).

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12 p.: ill.

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Mei, Jiajun; Carsch, Kurtis M.; Freitag, Cody R.; Gunnoe, T. Brent & Cundari, Thomas R., 1964- December 24, 2012.

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Article discussing variable pathways for oxygen atom insertion into metal-carbon bonds and the case of Cp*W(O)2(CH2SiMe3).

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12 p.: ill.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2013 American Chemical Society.

Abstract: Cp*W(O)₂(CH₂SiMe₃) (1) (Cp* = η⁵-pentamethylcyclopentadienyl) reacts with oxygen atom donors (e.g., H₂O₂, PhIO, IO₄⁻) in THF/water to produce TMSCH₂OH (TMS = trimethylsilyl). For the reaction of 1 with IO₄⁻, the proposed pathway for alcohol formation involves coordination of IO₄⁻ to 1 followed by concerted migration of the -CH₂TMS ligand to the coordinated oxygen of IO₄⁻ with concomitant dissociation of IO₃⁻ to produce Cp*W(O)₂(OCH₂SiMe₃) (3), which undergoes protonolysis to yield free alcohol. In contrast to the reaction with IO₄⁻, the reaction of 1 with H₂O₂ results in the formation of the η²-peroxo complex Cp*W(O)(η²-O₂)(CH₂SiMe₃) (2). In the presence of acid (HCl) or base (NaOH), complex 2 produces TMSCH₂OH. The conversion of 2 to TMSCH₂OH catalyzed by Brønsted acid is proposed to occur through protonation of the η²-peroxo ligand, which facilitates the transfer of the -CH₂TMS ligand to a coordinated oxygen of the η²-hydroperoxo ligand. In contrast, the hydroxide promoted conversion of 2 to TMSCH₂OH is proposed to involve hydroxide coordination, followed by proton transfer fro the hydroxide ligand to the peroxide ligand to yield a κ¹-hydroperoxide intermediate. The migration of the -CH₂TMS ligand to the coordinated oxygen of the κ¹-hydroperoxo produces an alkoxide complex, which undergoes protonolysis to yield free alcohol.

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  • Journal of the American Chemical Society, 2013, Washington DC: American Chemical Society, pp. 424-435

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 135
  • Issue: 1
  • Page Start: 424
  • Page End: 435
  • Peer Reviewed: Yes

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  • December 24, 2012

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  • Aug. 30, 2013, 3:35 p.m.

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  • May 27, 2014, 4:21 p.m.

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Mei, Jiajun; Carsch, Kurtis M.; Freitag, Cody R.; Gunnoe, T. Brent & Cundari, Thomas R., 1964-. Variable Pathways for Oxygen Atom Insertion into Metal-Carbon Bonds: The Case of Cp*W(O)₂(CH₂SiMe₃), article, December 24, 2012; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc179685/: accessed August 16, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.