Arylpalladium Phosphonate Complexes as Reactive Intermediates in Phosphorus-Carbon Bond Forming Reactions

Description:

Article discussing research on arylpalladium phosphonate complexes as reactive intermediates in phosphorus-carbon bond forming reactions.

Creator(s):
Creation Date: January 21, 2009
Partner(s):
UNT College of Arts and Sciences
Collection(s):
UNT Scholarly Works
Usage:
Total Uses: 223
Past 30 days: 1
Yesterday: 0
Creator (Author):
Kohler, Mark C.

Bucknell University

Creator (Author):
Grimes, Thomas V.

University of North Texas; Kyoto University

Creator (Author):
Wang, Xiaoping

University of North Texas

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

University of North Texas

Creator (Author):
Stockland, Robert A., Jr.

Bucknell University

Publisher Info:
Publisher Name: American Chemical Society
Place of Publication: [Washington, DC]
Date(s):
  • Creation: January 21, 2009
Description:

Article discussing research on arylpalladium phosphonate complexes as reactive intermediates in phosphorus-carbon bond forming reactions.

Degree:
Department: Chemistry
Note:

Reprinted with permission from Organometallics. Copyright 2009 American Chemical Society.

Note:

Abstract: Phosphorus-carbon bond formation from discrete transition metal complexes have been investigated through a combination of synthetic, spectroscopic, crystallographic, and computational methods. Reactive intermediates of the type (diphosphine)Pd(aryl)P(O)(OEt)2) have been prepared, characterized, and studied as possible intermediates in metal-mediated coupling reactions. Several of the reactive intermediates were characterized crystallographically, and a discussion of the solid state structures is presented. In contrast to other carbon-heteroelement bond forming reactions, palladium complexes containing electron-donating substituents on the aromatic fragment exhibited faster rates of reductive elimination. Large bit angle diphosphine ligands induced rapid rates of elimination, while bipyridine and small bite angle diphosphine ligands resulted in much slower rates of elimination. An investigation of the effect of typical impurities on the elimination reaction was carried out. While excess diphosphine, pyridine, and acetonitrile had little effect on the observed rate, the addition of water slowed the phosphorus-carbon bond forming reaction. Coordination of water to the complex was observed spectroscopically and crystallographically. Computational studies were utilized to probe the reaction pathways for P-C bond formation via Pd catalysis.

Physical Description:

9 p.

Language(s):
Subject(s):
Keyword(s): phosphorus-carbon bonds | transition metal complexes | diphosphine ligands
Source: Organometallics, 2009, Washington DC: American Chemical Society, pp. 1193-1201
Partner:
UNT College of Arts and Sciences
Collection:
UNT Scholarly Works
Identifier:
  • DOI: 10.1021/om800906m |
  • ARK: ark:/67531/metadc77191
Resource Type: Article
Format: Text
Rights:
Access: Public
Citation:
Publication Title: Organometallics
Volume: 28
Page Start: 1193
Page End: 1201
Pages: 9
Peer Reviewed: Yes