Neutral (bis-beta-diketonato) iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) metallocycles: structural, electrochemical and solvent extraction studies

Clegg, Jack K., Bray, David J., Gloe, Kerstin, Gloe, Karsten, Hayter, Michael J., Jolliffe, Katrina A., Lawrance, Geoffrey A., Meehan, George V., McMurtrie, John C., Lindoy, Leonard F. and Wenzel, Marco (2007) Neutral (bis-beta-diketonato) iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) metallocycles: structural, electrochemical and solvent extraction studies. Dalton Transactions, 17: 1719-1730. doi:10.1039/b701575e

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Author Clegg, Jack K.
Bray, David J.
Gloe, Kerstin
Gloe, Karsten
Hayter, Michael J.
Jolliffe, Katrina A.
Lawrance, Geoffrey A.
Meehan, George V.
McMurtrie, John C.
Lindoy, Leonard F.
Wenzel, Marco
Title Neutral (bis-beta-diketonato) iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) metallocycles: structural, electrochemical and solvent extraction studies
Journal name Dalton Transactions   Check publisher's open access policy
ISSN 1477-9226
1477-9234
Publication date 2007-01
Sub-type Article (original research)
DOI 10.1039/b701575e
Open Access Status File (Publisher version)
Issue 17
Start page 1719
End page 1730
Total pages 12
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted abstract
Neutral dimeric metallocyclic complexes of type [M 2(L 1) 2B n] (where M = cobalt(ii), nickel(ii) and zinc(ii), L 1 is the doubly deprotonated form of a 1,3-aryl linked bis-β-diketone ligand of type 1,3-bis(RC(O)CH 2C(O))C 6H 4 (R = Me, n-Pr, t-Bu) and B is pyridine (Py) or 4-ethylpyridine (EtPy)) have been synthesised, adding to similar complexes already reported for copper(ii). New lipophilic ligand derivatives with R = octyl or nonyl were also prepared for use in solvent extraction experiments. Structural, electrochemical and solvent extraction investigations of selected metal complex systems from the above series are reported, with the X-ray structures of [Co 2(L 1) 2(Py) 4] ·2.25CHCl 3·0.5H 2O (R = Pr), [Co 2(L 1) 2(EtPy) 4] (R = t-Bu), [Ni 2(L 1) 2(EtPy) 4] (R = t-Bu), [Zn 2(L 1) 2(EtPy) 2] (R = Me) and [Zn 2(L 1) 2(EtPy) 4] (R = t-Bu) being presented. The electrochemistry of H 2L 1 (R = t-Bu) and of [Fe 2(L 1) 3], [Co 2(L 1) 2(Py) 4], [Ni 2(L 1) 2(Py) 4], [Cu 2(L 1) 2] and [Zn 2(L 1) 2(Py) 2] has been examined. Oxidative processes for the complexes are dominantly irreversible, but several examples of quasireversible behaviour were observed and support the assignment of an anodic process, seen between +1.0 and +1.6 V, as a metal-centred oxidation. The reduction processes for the respective metal complexes are not simple, and irreversible in most cases. Solvent extraction studies (water/chloroform) involving variable concentrations of metal, bis-β-diketone and heterocyclic base have been performed for cobalt(ii) and zinc(ii) using a radiotracer technique to probe the stoichiometries of the extracted species in each case. Synergism was observed when 4-ethylpyridine was added to the bis-β-diketone ligand in the chloroform phase. Competitive extraction studies show a clear uptake preference for copper(ii) over cobalt(ii), nickel(ii), zinc(ii) and cadmium(ii).
Keyword Supramolecular structures
Lanthanide complexes
Crystal structure
Metal complexes
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ
Additional Notes First published on the web 26 March 2007.

Document type: Journal Article
Sub-type: Article (original research)
Collection: School of Chemistry and Molecular Biosciences
 
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