Kershaw Cook, LJ, Kulmaczewski, R orcid.org/0000-0002-3855-4530, Mohammed, R et al. (5 more authors) (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. ISSN 1433-7851
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 (T1/2) 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 T1/2 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.
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Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | © 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
Keywords: | density functional calculations; iron; N ligands; spin state; substituent effects |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Inorganic Chemistry (Leeds) |
Funding Information: | Funder Grant number EPSRC EP/F006691/1 EPSRC EP/H015639/1 EPSRC EP/K012568/1 |
Depositing User: | Symplectic Publications |
Date Deposited: | 19 Feb 2016 16:42 |
Last Modified: | 23 Jun 2023 21:59 |
Published Version: | http://dx.doi.org/10.1002/anie.201600165 |
Status: | Published |
Publisher: | Wiley |
Identification Number: | 10.1002/anie.201600165 |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:95030 |
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