Kershaw Cook, LJ, Fisher, J, Harding, LP et al. (1 more author) (2015) An iron(ii) spin-crossover metallacycle from a back-to-back bis-[dipyrazolylpyridine]. Dalton Transactions. ISSN 1477-9226
Abstract
The syntheses of 4-mercapto-2,6-di(pyrazol-1-yl)pyridine (bppSH) and bis[2,6-di(pyrazol-1-yl)pyrid-4-yl]disulfide (bppSSbpp) are reported. In contrast to previously published "back-to-back" bis-[2,6-di(pyrazol-1-yl)pyridine] derivatives, which form coordination polymers with transition ions that are usually insoluble, bppSSbpp yields soluble oligomeric complexes with iron(ii) and zinc(ii). Mass spectrometry and DOSY data show that [{Fe(μ-bppSSbpp)}n](2n+) and [{Zn(μ-bppSSbpp)}n](2n+) form tetranuclear metallacycles in nitromethane solution (n = 4), although (1)H NMR and conductivity measurements imply the iron compound may undergo more fragmentation than its zinc congener. Both [{Fe(bppSH)2](2+) and [{Fe(μ-bppSSbpp)}n](2n+) exhibit thermal spin-crossover in CD3NO2 solution, with midpoint temperatures near 245 K. The similarity of these equilibria implies there is little cooperativity between the iron centres in the metallacyclic structures.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | (c) 2015, The Royal Society of Chemistry. This is an author produced version of a paper published in Dalton Transactions. Uploaded in accordance with the publisher's self-archiving policy |
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) |
Depositing User: | Symplectic Publications |
Date Deposited: | 05 May 2015 12:41 |
Last Modified: | 01 May 2016 06:26 |
Published Version: | http://dx.doi.org/10.1039/c5dt00732a |
Status: | Published |
Publisher: | Royal Society of Chemistry |
Identification Number: | 10.1039/c5dt00732a |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:85597 |