Synthetic, structural, electrochemical and solvent extraction studies of neutral trinuclear Co(II), Ni(II), Cu(II) and Zn(II) metallocycles and tetrahedral tetranuclear Fe(III) species incorporating 1,4-aryl-linked bis-beta-diketonato ligands

Clegg, Jack K., Bray, David J., Gloe, Kerstin, Gloe, Karsten, Jolliffe, Katrina A., Lawrance, Geoffrey A., Lindoy, Leonard F., Meehane, George V. and Wenzelb, Marco (2008) Synthetic, structural, electrochemical and solvent extraction studies of neutral trinuclear Co(II), Ni(II), Cu(II) and Zn(II) metallocycles and tetrahedral tetranuclear Fe(III) species incorporating 1,4-aryl-linked bis-beta-diketonato ligands. Dalton Transactions, 10: 1331-1340. doi:10.1039/b716653b

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Author Clegg, Jack K.
Bray, David J.
Gloe, Kerstin
Gloe, Karsten
Jolliffe, Katrina A.
Lawrance, Geoffrey A.
Lindoy, Leonard F.
Meehane, George V.
Wenzelb, Marco
Title Synthetic, structural, electrochemical and solvent extraction studies of neutral trinuclear Co(II), Ni(II), Cu(II) and Zn(II) metallocycles and tetrahedral tetranuclear Fe(III) species incorporating 1,4-aryl-linked bis-beta-diketonato ligands
Journal name Dalton Transactions   Check publisher's open access policy
ISSN 1477-9226
1477-9234
Publication date 2008-01
Sub-type Article (original research)
DOI 10.1039/b716653b
Open Access Status File (Publisher version)
Issue 10
Start page 1331
End page 1340
Total pages 10
Place of publication Cambridge, United Kingdom
Publisher Royal Society of Chemistry
Language eng
Formatted abstract
Uncharged complexes, formulated as trimeric metallocycles of type [M 3(L 1) 3(Py) 6] (where M = cobalt(ii), nickel(ii) and zinc(ii) and L 1 is the doubly deprotonated form of a 1,4-phenylene linked bis-β-diketone ligand of type 1,4-bis(RC(O)CH 2C(O))C 6H 4 (R = t-Bu)) have been synthesised, adding to related, previously reported complexes of these metals with L 1 (R = Ph) and copper(ii) with L 1 (R = Me, Et, Pr, t-Bu, Ph). New lipophilic ligand derivatives with R = hexyl, octyl or nonyl were also prepared for use in solvent extraction experiments. The X-ray structures of H 2L 1 (R = t-Bu) and of its trinuclear (triangular) nickel(ii) complex [Ni 3(L 1) 3(Py) 6]•3.5Py (R = t-Bu) are also presented. Electrochemical studies of H 2L 1, [Co 3(L 1) 3(Py) 6], [Ni 3(L 1) 3(Py) 6], [Cu 3(L 1) 3], [Zn 3(L 1) 3(Py) 6] and [Fe 4(L 1) 6] (all with R = t-Bu) show that oxidative processes for the complexes are predominantly irreversible, but several examples of quasireversible behaviour also occur and support the assignment of an anodic process, seen between +1.0 and +1.6 V, as involving metal-centred oxidations. The reduction behaviour for the respective metal complexes is not simple, being irreversible in most cases. Solvent extraction studies (water/chloroform) involving the systematic variation of the metal, bis-β-diketone and heterocyclic base concentrations have been performed for cobalt(ii) and zinc(ii) using a radiotracer technique in order to probe the stoichiometries of the respective extracted species. Significant extraction synergism was observed when 4-ethylpyridine was also present with the bis-β-diketone ligand in the chloroform phase. Competitive extraction studies demonstrated a clear uptake preference for copper(ii) over cobalt(ii), nickel(ii), zinc(ii) and cadmium(ii).
Keyword Chelate complexes
Supramolecular chemistry
Building blocks
Copper(ii) metallocycles
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Non-UQ
Additional Notes First published on the web 16 January 2008.

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