English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT
  Effect of N-Methylation of Macrocyclic Amine Ligands on the Spin State of Iron(III):  A Tale of Two Fluoro Complexes

Berry, J. F., Bill, E., García-Serres, R., Neese, F., Weyhermüller, T., & Wieghardt, K. (2006). Effect of N-Methylation of Macrocyclic Amine Ligands on the Spin State of Iron(III):  A Tale of Two Fluoro Complexes. Inorganic Chemistry, 45(5), 2027-2037. doi:10.1021/ic051823y.

Item is

Basic

show hide
Genre: Journal Article

Files

show Files

Locators

show

Creators

show
hide
 Creators:
Berry, John F.1, Author              
Bill, Eckhard1, Author              
García-Serres, Ricardo1, Author
Neese, Frank1, Author              
Weyhermüller, Thomas1, Author              
Wieghardt, Karl1, Author              
Affiliations:
1Research Department Wieghardt, Max Planck Institute for Bioinorganic Chemistry, Max Planck Society, ou_3023881              

Content

show
hide
Free keywords: -
 Abstract: Syntheses and characterization of [(cyclamacetate)FeF]PF6 (1) and the corresponding N-methylated complex [(trimethylcyclamacetate)FeF]PF6 (3) are presented. Compound 1 is prepared in good yields from the analogous chloro complex, whereas 3 is prepared by hydrolysis of the oxo-bridged diiron compound (Me3cyclam-acetate)Fe−O−FeCl3 (2) in the presence of PF6 anions. Magnetic susceptibility and spectroscopic data including electron paramagnetic resonance and Mössbauer spectra indicate that 1 contains low-spin FeIII (S = 1/2), while 3 is high spin (S = 5/2). Both octahedral fluoro complexes were investigated theoretically by density functional theory in order to determine why the spin states of the two molecules are different. Energies calculated using the B3LYP functional correctly predict 1 to have a low-spin S = 1/2 ground state and 3 to be high spin, regardless of whether a solvation model is included. The difference between 1 and 3 is most likely a combination of steric effects caused by the N-methyl groups, which compel the Fe−N bond distances to be longer in 3 than they ordinarily would be, and also electronic effects, which cause the N-methylated ligand to be a weaker σ donor than its nonmethylated counterpart.

Details

show
hide
Language(s): eng - English
 Dates: 2005-10-212006-01-202006-03-01
 Publication Status: Published in print
 Pages: 11
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/ic051823y
 Degree: -

Event

show

Legal Case

show

Project information

show

Source 1

show
hide
Title: Inorganic Chemistry
  Abbreviation : Inorg. Chem.
Source Genre: Journal
 Creator(s):
Affiliations:
Publ. Info: Washington, DC : American Chemical Society
Pages: - Volume / Issue: 45 (5) Sequence Number: - Start / End Page: 2027 - 2037 Identifier: ISSN: 0020-1669
CoNE: https://pure.mpg.de/cone/journals/resource/0020-1669