Reductive Elimination of Alkylamines from Low-Valent, Alkylpalladium(II) Amido Complexes

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This article discusses reductive elimination of alkylamines from low-valent, alkylpalladium(II) amido complexes.

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4 p.

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Hanley, Patrick S.; Marquard, Seth L.; Cundari, Thomas R., 1964- & Hartwig, John F. August 30, 2012.

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This article discusses reductive elimination of alkylamines from low-valent, alkylpalladium(II) amido complexes.

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4 p.

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Reprinted with permission from the Journal of the American Chemical Society. Copyright 2012 American Chemical Society.

Abstract: A series of three-coordinate norbornylpalladium amido complexes ligated by bulky N-heterocyclic carbene (NHC) ligands were prepared that undergo reductive eliminations to form the alkyl-nitrogen bond of alkylamine products. The rates of reductive elimination reveal that complexes containing more-electron-donating amido groups react faster than those with less-electron-donating amido groups, and complexes containing more-sterically bulky amido groups undergo reductive elimination more slowly than complexes containing less-sterically bulky amido groups. Complexes ligated by more-electron-donating ancillary NHC ligands undergo reductive elimination faster than complexes ligated by less-electron-donating NHC ligands. In contrast to the reductive elimination of benzylamines from bisphosphine-ligated palladium amides, these reactions occur with retention of configuration at the alkyl group, indicating that these reductive eliminations proceed by a concerted pathway. The experimentally determined free energy barrier of 26 kcal/mol is close to the computed free energy barrier of 23.9 kcal/mol (363 K) for a concerted reductive elimination from the isolated, three-coordinate NHC-ligated palladium anilido complex.

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  • Journal of the American Chemical Society, 2012, Washington DC: American Chemical Society, pp. 15281-15284

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  • Publication Title: Journal of the American Chemical Society
  • Volume: 134
  • Issue: 37
  • Page Start: 15281
  • Page End: 15284
  • Peer Reviewed: Yes

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The Scholarly Works Collection is home to materials from the University of North Texas community's research, creative, and scholarly activities and serves as UNT's Open Access Repository. It brings together articles, papers, artwork, music, research data, reports, presentations, and other scholarly and creative products representing the expertise in our university community.** Access to some items in this collection may be restricted.**

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  • August 30, 2012

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  • Oct. 9, 2012, 10:02 a.m.

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  • April 1, 2014, 2:54 p.m.

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Hanley, Patrick S.; Marquard, Seth L.; Cundari, Thomas R., 1964- & Hartwig, John F. Reductive Elimination of Alkylamines from Low-Valent, Alkylpalladium(II) Amido Complexes, article, August 30, 2012; [Washington, D.C.]. (digital.library.unt.edu/ark:/67531/metadc107792/: accessed February 21, 2017), University of North Texas Libraries, Digital Library, digital.library.unt.edu; crediting UNT College of Arts and Sciences.