Carbon-Oxygen Bond Formation via Organometallic Baeyer-Villiger Transformations: A Computational Study on the Impact of Metal Identity

Description:

Article discussing a computational study on the impact of metal identity and carbon-oxygen bond formation via organometallic Baeyer-Villiger transformations.

Creator(s):
Creation Date: December 20, 2011
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
Usage:
Total Uses: 162
Past 30 days: 3
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Creator (Author):
Figg, Travis M.

University of North Texas

Creator (Author):
Webb, Joanna R.

University of Virginia

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

University of North Texas

Creator (Author):
Gunnoe, T. Brent

University of Virginia

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: December 20, 2011
Description:

Article discussing a computational study on the impact of metal identity and carbon-oxygen bond formation via organometallic Baeyer-Villiger transformations.

Degree:
Department: Chemistry
Note:

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

Note:

Abstract: Metal-mediated formation of C-O bonds is an important transformation that can occur by a variety of mechanisms. Recent studies suggest that oxygen-atom insertion into metal-hydrocarbyl bonds in a reaction that resembles the Baeyer-Villiger transformation is a viable process. In an effort to identify promising new systems, this study is designed to assess the impact of metal identity on such O-atom insertions for the reaction [(bpy)ₓM(Me)(OOH)]ⁿ → [(bpy)ₓM(OMe)(OH)]ⁿ (x = 1 or 2; bpy = 2,2'-bipyridyl; n is varied to maintain the d-electron count at d⁶ or d⁸). Six d⁸-square-planar complexes (M = Ptᴵᴵ, Pdᴵᴵ, Niᴵᴵ, Irᴵ, Rhᴵ, and Coᴵ) and eight d⁶-octahedral systems (M = Irᴵᴵᴵ, Rhᴵᴵᴵ, Coᴵᴵᴵ, Feᴵᴵ, Ruᴵᴵ, Osᴵᴵ, Mnᴵ, and Tcᴵ) are studied. Using density functional theory calculations, the structures and energies of ground-state and transition-state species are elucidated. This study shows clear trends in calculated ∆G‡'s for the O-atom insertions. The organometallic Baeyer-Villiger insertions are favored by lower coordination numbers (x = 1 versus x = 2), earlier transition metals, and first-row (3d) transition metals.

Physical Description:

8 p.

Language(s):
Subject(s):
Keyword(s): carbon-oxygen bonds | metal identity | density functional theory
Source: Journal of the American Chemical Society, 2012, Washington DC: American Chemical Society, pp. 2332-2339
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/ja2102778 |
  • ARK: ark:/67531/metadc107789
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Journal of the American Chemical Society
Volume: 134
Issue: 4
Page Start: 2332
Page End: 2339
Peer Reviewed: Yes