Single-Electron Oxidation of Monomeric Copper(I) Alkyl Complexes: Evidence for Reductive Elimination through Biomolecular Formation of Alkanes

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This article discusses single-electron oxidation of monomeric copper(I) alkyl complexes.

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8 p.

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Goj, Laurel A.; Blue, Elizabeth D.; Delp, Samuel A.; Gunnoe, T. Brent; Cundari, Thomas R., 1964- & Petersen, Jeffrey L. July 21, 2006.

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This article discusses single-electron oxidation of monomeric copper(I) alkyl complexes.

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8 p.

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Reprinted with permission from Organometallics. Copyright 2006 American Chemical Society.

Abstract: Monomeric Cu(I) alkyl complexes (NHC)Cu(R) (NHC = N-heterocyclic carbene; R = Me or Et) and (dtbpe)Cu(Me) (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) have been prepared, isolated, and characterized. Single-electron oxidation of the Cu(I) alkyl complexes upon reaction with AgOTf to form putative Cu(II) intermediates of the type [(L)Cu(R)]+ (L = NHC or dtbpe, R = Me or Et) results in the rapid production of (L)Cu(X) (X = OTf) and R2. Experimental studies suggest that the reductive elimination of R2 from Cu(II) occurs through a nonradical bimolecular mechanism. Computational studies of the Cu-Cmethyl yield bond dissocation enthalpies of [(SIPr)Cu-CH3]n+ (80 kcal/mol for n = 0 {Cu(I)} and 38 kcal/mol for n = 1 {Cu(II)}).

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  • Organometallics, 2006, Washington DC: American Chemical Society, pp. 4097-4104

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  • Publication Title: Organometallics
  • Volume: 25
  • Page Start: 4097
  • Page End: 4104
  • Pages: 8
  • Peer Reviewed: Yes

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  • July 21, 2006

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  • March 9, 2012, 2:17 p.m.

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Goj, Laurel A.; Blue, Elizabeth D.; Delp, Samuel A.; Gunnoe, T. Brent; Cundari, Thomas R., 1964- & Petersen, Jeffrey L. Single-Electron Oxidation of Monomeric Copper(I) Alkyl Complexes: Evidence for Reductive Elimination through Biomolecular Formation of Alkanes, article, July 21, 2006; [Washington, D.C.]. (https://digital.library.unt.edu/ark:/67531/metadc77186/: accessed July 18, 2024), University of North Texas Libraries, UNT Digital Library, https://digital.library.unt.edu; crediting UNT College of Arts and Sciences.

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