Pubfacts - Scientific Publication Data
  • Categories
  • |
  • Journals
  • |
  • Authors
  • Login
  • Categories
  • Journals

Search Our Scientific Publications & Authors

Publications
  • Publications
  • Authors
find publications by category +
Translate page:

Activation of aldehydes by exocyclic iridium(i)-η:π-diene complexes derived from 1,3-oxazolidin-2-ones.

Authors:
Rosa Padilla Verónica Salazar-Pereda Daniel Mendoza-Espinosa José M Vásquez-Pérez Noemí Andrade-López Joaquín Tamariz José G Alvarado-Rodríguez Julián Cruz-Borbolla

Dalton Trans 2016 Nov 29;45(42):16878-16888. Epub 2016 Sep 29.

Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Carretera Pachuca-Tulancingo Km. 4.5, Mineral de la Reforma, Hidalgo 42090, México.

The Ir(i) complexes [TpIr(η-1,4-diene)] 2b and 2c react thermally with a variety of aromatic aldehydes, 3a-e, to generate the metallabicyclic compounds 4e-k and the Fischer-type carbenes 5a-b in moderate yields. These reactions are proposed to take place with the initial formation of η-aldehyde adducts as key intermediates. The formation of the metallabicyclic compounds 4e-k involves a formal decarboxylation process at the exo-2-oxazolidinone diene and an ortho metallation of the aromatic ring. The generation of the Fischer-type carbenes 5a-b is the result of a series of metal-based rearranged intermediates with no decarboxylation observed. Treatment of the η-diene complex 2b with a variety of Lewis bases induces a change in the binding mode of the diene ligand from η:π to η:σ to form the Ir(iii) derivatives 6b-d of composition TpIr-(η:π-1,4-diene)(L) (L = CO, MeCN, and CHN). A study of reactions of complex 2b with either mono- or poly-deuterated aldehydes was performed to understand the mechanisms of such processes. The results of these studies were used to determine plausible formation mechanisms of the metallabicyclic compounds 4e-4k and Fischer-type carbenes 5a-b compound series. These mechanisms were corroborated by density functional theory (DFT) calculations of the free energy profiles.

Download full-text PDF

Source
http://dx.doi.org/10.1039/c6dt02866gDOI Listing
November 2016

Publication Analysis

Top Keywords

metallabicyclic compounds
12
fischer-type carbenes
12
carbenes 5a-b
12
compounds 4e-k
8
binding mode
4
lewis bases
4
bases induces
4
induces change
4
change binding
4
ligand ηπ
4
mode diene
4
diene ligand
4
complex variety
4
ηπ ησ
4
ησ form
4
form iriii
4
variety lewis
4
η-diene complex
4
derivatives 6b-d
4
generation fischer-type
4

Keyword Occurance

Similar Publications

Activation of aldehydes by exocyclic iridium(i)-η:π-diene complexes derived from 1,3-oxazolidin-2-ones.

Authors:
Rosa Padilla Verónica Salazar-Pereda Daniel Mendoza-Espinosa José M Vásquez-Pérez Noemí Andrade-López Joaquín Tamariz José G Alvarado-Rodríguez Julián Cruz-Borbolla

Dalton Trans 2016 Nov 29;45(42):16878-16888. Epub 2016 Sep 29.

Área Académica de Química, Universidad Autónoma del Estado de Hidalgo, Carretera Pachuca-Tulancingo Km. 4.5, Mineral de la Reforma, Hidalgo 42090, México.

The Ir(i) complexes [TpIr(η-1,4-diene)] 2b and 2c react thermally with a variety of aromatic aldehydes, 3a-e, to generate the metallabicyclic compounds 4e-k and the Fischer-type carbenes 5a-b in moderate yields. These reactions are proposed to take place with the initial formation of η-aldehyde adducts as key intermediates. The formation of the metallabicyclic compounds 4e-k involves a formal decarboxylation process at the exo-2-oxazolidinone diene and an ortho metallation of the aromatic ring. Read More

View Article and Full-Text PDF
November 2016
Similar Publications

trans-RhCl(CO)(PPh3)2-catalyzed monomeric and dimeric cycloisomerization of propargylic 2,3-dienoates. Establishment of alpha,beta-unsaturated delta-lactone rings by cyclometallation.

Authors:
Xuefeng Jiang Shengming Ma

J Am Chem Soc 2007 Sep 29;129(37):11600-7. Epub 2007 Aug 29.

State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Lu, Shanghai 200032, P. R. China.

Cyclometallation of two unsaturated carbon-carbon bonds usually requires the application of low-valent metal catalysts, which could cleave the propargylic ester linkage. Thus, it is desirable to identify a catalyst which could undergo cyclometallation without cleaving the propargylic ester linkage. In this paper, we used trans-RhCl(CO)(PPh(3))(2) to realize the cyclometallation of propargylic 2,3-dienoates. Read More

View Article and Full-Text PDF
September 2007
Similar Publications
}
© 2022 PubFacts.
  • About PubFacts
  • Privacy Policy
  • Sitemap