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

Description:

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

Creator(s):
Creation Date: August 30, 2012
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
Usage:
Total Uses: 117
Past 30 days: 13
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Creator (Author):
Hanley, Patrick S.

University of Illinois at Urbana-Champaign

Creator (Author):
Marquard, Seth L.

University of Illinois at Urbana-Champaign

Creator (Author):
Cundari, Thomas R., 1964-

University of North Texas

Creator (Author):
Hartwig, John F.

University of Illinois at Urbana-Champaign; University of California

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, D.C.]
Date(s):
  • Creation: August 30, 2012
Description:

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

Degree:
Department: Chemistry
Note:

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

Note:

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.

Physical Description:

4 p.

Language(s):
Subject(s):
Keyword(s): alkylamines | amido complexes | ligands | N-heterocyclic carbene | NHC
Source: Journal of the American Chemical Society, 2012, Washington DC: American Chemical Society, pp. 15281-15284
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja307558x
  • ARK: ark:/67531/metadc107792
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 134
Issue: 37
Page Start: 15281
Page End: 15284
Peer Reviewed: Yes