English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Reversible C–C Bond Formation between Redox-Active Pyridine Ligands in Iron Complexes

Dugan, T. R., Bill, E., MacLeod, K. C., Christian, G. J., Cowley, R. E., Brennessel, W. W., et al. (2012). Reversible C–C Bond Formation between Redox-Active Pyridine Ligands in Iron Complexes. Journal of the American Chemical Society, 134(50), 20352-20364. doi:10.1021/ja305679m.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Dugan, Thomas R.1, Author
Bill, Eckhard2, Author              
MacLeod, K. Cory1, Author
Christian, Gemma J.2, Author
Cowley, Ryan E.1, Author
Brennessel, William W.1, Author
Ye, Shengfa2, Author              
Neese, Frank2, Author              
Holland, Patrick L.1, Author
Affiliations:
1Department of Chemistry, University of Rochester, Rochester, New York, ou_persistent22              
2Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society, ou_3023886              

Content

show
hide
Free keywords: -
 Abstract: This manuscript describes the formally iron(I) complexes LMeFe(Py-R)2 (LMe = bulky β-diketiminate; R = H, 4-tBu), in which the basal pyridine ligands preferentially accept significant unpaired spin density. Structural, spectroscopic, and computational studies on the complex with 4-tert-butylpyridine (tBupy) indicate that the S = 3/2 species is a resonance hybrid between descriptions as (a) high-spin iron(II) with antiferromagnetic coupling to a pyridine anion radical and (b) high-spin iron(I). When the pyridine lacks the protection of the tert-butyl group, it rapidly and reversibly undergoes radical coupling reactions that form new C–C bonds. In one reaction, the coordinated pyridine couples to triphenylmethyl radical, and in another, it dimerizes to give a pyridine-derived dianion that bridges two iron(II) ions. The rapid, reversible C–C bond formation in the dimer stores electrons from the formally reduced metal as a C–C bond in the ligands, as demonstrated by using the coupled diiron(II) complex to generate products that are known to come from iron(I) precursors.

Details

show
hide
Language(s): eng - English
 Dates: 2012-06-122012-12-112012-12-19
 Publication Status: Published in print
 Pages: 13
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ja305679m
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Journal of the American Chemical Society
  Other : JACS
  Abbreviation : J. Am. Chem. Soc.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 134 (50) Sequence Number: - Start / End Page: 20352 - 20364 Identifier: ISSN: 0002-7863
CoNE: https://pure.mpg.de/cone/journals/resource/954925376870