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-β-diketonato ligands

被引:42
作者
Clegg, Jack K. [1 ]
Bray, David J. [1 ]
Gloe, Kerstin [2 ]
Gloe, Karsten [2 ]
Jolliffe, Katrina A. [3 ]
Lawrance, Geoffrey A. [5 ]
Lindoy, Leonard F. [1 ]
Meehane, George V. [4 ]
Wenzelb, Marco [2 ]
机构
[1] Univ Sydney, Sch Chem, Ctr Heavy Met Res, Sydney, NSW 2006, Australia
[2] Tech Univ Dresden, Dept Chem & Food Chem, D-01062 Dresden, Germany
[3] Univ Sydney, Sch Chem, Sydney, NSW 2006, Australia
[4] James Cook Univ N Queensland, Sch Pharm & Mol Sci, Townsville, Qld 4811, Australia
[5] Univ Newcastle, Sch Environm & Life Sci, Discipline Chem, Newcastle, NSW 2308, Australia
关键词
D O I
10.1039/b716653b
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
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-beta-diketone ligand of type 1,4-bis(RC(O)CH2C(O))C6H4 (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 H2L1 (R = t-Bu) and of its trinuclear (triangular) nickel(II) complex [Ni-3(L-1)(3)(Py)(6)]center dot 3.5Py (R = t-Bu) are also presented. Electrochemical studies of H2L1, [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-beta-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-beta-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).
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收藏
页码:1331 / 1340
页数:10
相关论文
共 71 条
  • [1] Self-assembly of an unpolar enantiomerically pure helicate-type metalla-cryptand
    Albrecht, M
    Schmid, S
    deGroot, M
    Weis, P
    Fröhlich, R
    [J]. CHEMICAL COMMUNICATIONS, 2003, (20) : 2526 - 2527
  • [2] Enantiomerically pure bis-β-diketones:: Valuable building blocks for metallosupramolecular chemistry
    Albrecht, Markus
    Dehn, Sabrina
    Schmid, Soeren
    DeGroot, Marita
    [J]. SYNTHESIS-STUTTGART, 2007, (01): : 155 - 158
  • [3] SIR97:: a new tool for crystal structure determination and refinement
    Altomare, A
    Burla, MC
    Camalli, M
    Cascarano, GL
    Giacovazzo, C
    Guagliardi, A
    Moliterni, AGG
    Polidori, G
    Spagna, R
    [J]. JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1999, 32 : 115 - 119
  • [4] [Anonymous], 1999, J. Appl. Crystallogr, DOI [DOI 10.1107/S0021889899006020, 10.1107/S0021889899006020]
  • [5] Aggregation of [CuII4] building blocks into [CuII8] clusters or a [CuII4]∞ chain through subtle chemical control
    Aromí, G
    Ribas, J
    Gamez, P
    Roubeau, O
    Kooijman, H
    Spek, AL
    Teat, S
    MacLean, E
    Stoeckli-Evans, H
    Reedijk, J
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 2004, 10 (24) : 6476 - 6488
  • [6] Complexes of a novel multinucleating poly-β-diketonate ligand
    Aromi, G
    Boldron, C
    Gamez, P
    Roubeau, O
    Kooijman, H
    Spek, AL
    Stoeckli-Evans, H
    Ribas, J
    Reedijk, J
    [J]. DALTON TRANSACTIONS, 2004, (21) : 3586 - 3592
  • [7] Two new bis-β-diketones as ligands for novel systems in supramolecular chemistry
    Aromí, G
    Gamez, P
    Berzal, PC
    Driessen, WL
    Reedijk, J
    [J]. SYNTHETIC COMMUNICATIONS, 2003, 33 (01) : 11 - 18
  • [8] A solvent-controlled switch of manganese complex assemblies with a β-diketonate-based ligand
    Aromí, G
    Gamez, P
    Roubeau, O
    Berzal, PC
    Kooijman, H
    Spek, AL
    Driessen, WL
    Reedijk, J
    [J]. INORGANIC CHEMISTRY, 2002, 41 (14) : 3673 - 3683
  • [9] AROMI G, 2007, INORG CHEM, V46, P2579
  • [10] Poly beta-diketones:: Prime ligands to generate supramolecular metalloclusters
    Aromi, Guillem
    Gamez, Patrick
    Reedijk, Jan
    [J]. COORDINATION CHEMISTRY REVIEWS, 2008, 252 (8-9) : 964 - 989