The Library
A unified treatment of the relationship between ligand substituents and spin state in a family of iron(II) complexes
Tools
Kershaw Cook, Laurence J., Kulmaczewski, Rafal, Mohammed, Rufeida, Dudley, Stephen, Barrett, Simon A., Little, Marc A., Deeth, Robert J. and Halcrow, Malcolm A. (2016) A unified treatment of the relationship between ligand substituents and spin state in a family of iron(II) complexes. Angewandte Chemie International Edition, 55 (13). pp. 4327-4331. doi:10.1002/anie.201600165 ISSN 1433-7851.
|
PDF
WRAP_Kershaw-Cook_et_al-2016-Angewandte_Chemie_International_Edition.pdf - Published Version - Requires a PDF viewer. Available under License Creative Commons Attribution 4.0. Download (1556Kb) | Preview |
Official URL: http://dx.doi.org/10.1002/anie.201600165
Abstract
The influence of ligands on the spin state of a metal ion is of central importance for bioinorganic chemistry, and the production of base-metal catalysts for synthesis applications. Complexes derived from [Fe(bpp)2]2+ (bpp=2,6-di{pyrazol-1-yl}pyridine) can be high-spin, low-spin, or spin-crossover (SCO) active depending on the ligand substituents. Plots of the SCO midpoint temperature (Tinline image ) in solution vs. the relevant Hammett parameter show that the low-spin state of the complex is stabilized by electron-withdrawing pyridyl (“X”) substituents, but also by electron-donating pyrazolyl (“Y”) substituents. Moreover, when a subset of complexes with halogeno X or Y substituents is considered, the two sets of compounds instead show identical trends of a small reduction in Tinline image for increasing substituent electronegativity. DFT calculations reproduce these disparate trends, which arise from competing influences of pyridyl and pyrazolyl ligand substituents on Fe-L σ and π bonding.
Item Type: | Journal Article | ||||||||||
---|---|---|---|---|---|---|---|---|---|---|---|
Subjects: | Q Science > QD Chemistry | ||||||||||
Divisions: | Faculty of Science, Engineering and Medicine > Science > Chemistry | ||||||||||
Library of Congress Subject Headings (LCSH): | Bioinorganic chemistry -- Research, Electronegativity, Ligands, Metal ions, Electrons | ||||||||||
Journal or Publication Title: | Angewandte Chemie International Edition | ||||||||||
Publisher: | Wiley - V C H Verlag GmbH & Co. KGaA | ||||||||||
ISSN: | 1433-7851 | ||||||||||
Official Date: | 18 March 2016 | ||||||||||
Dates: |
|
||||||||||
Volume: | 55 | ||||||||||
Number: | 13 | ||||||||||
Page Range: | pp. 4327-4331 | ||||||||||
DOI: | 10.1002/anie.201600165 | ||||||||||
Status: | Peer Reviewed | ||||||||||
Publication Status: | Published | ||||||||||
Access rights to Published version: | Restricted or Subscription Access | ||||||||||
Date of first compliant deposit: | 9 May 2016 | ||||||||||
Date of first compliant Open Access: | 9 May 2016 | ||||||||||
Funder: | Engineering and Physical Sciences Research Council (EPSRC), European Cooperation in the Field of Scientific and Technical Research (Organization) (COST), University of Leeds | ||||||||||
Grant number: | EP/H015639/1, EP/F006691/1, EP/K012568/1, EP/K012940/1 and EP/K00512X/1 (EPSRC), Cost network CM1305 Explicit Control of Spin States in Technology and Biology (ECOSTBio) |
Request changes or add full text files to a record
Repository staff actions (login required)
View Item |
Downloads
Downloads per month over past year