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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Cyclam (1,4,8,11-tetraazacyclotetradecane) with one methylphosphonate pendant arm: a new ligand for selective copper(II) binding
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Cyclam (1,4,8,11-tetraazacyclotetradecane) with one methylphosphonate pendant arm: a new ligand for selective copper(II) binding

机译：Cyclam（1,4,8,11-四氮杂环十四烷）带有一个甲基膦酸酯侧链：选择性铜（II）结合的新配体

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摘要

The new ligand, [(1,4,8,11-tetraazacyclotetradecan-1-yl) methyl] phosphonic acid (H(2)te1P, H2L), was synthesized and its complexing properties towards selected metal ions were studied potentiometrically. The ligand forms a very stable complex with copper(II) (log beta(CuL) = 27.34), with a high selectivity over binding of other metal ions (i.e. log beta(ZnL) = 21.03). The crystal structures of the free ligand (in its protonated form with bromide as counter-ion) and two copper( II) complexes ( obtained by crystallization at various pH) were determined. The free ligand adopts the common conformation for such macrocycles with the protonated nitrogen atoms in the corners of a virtual rectangle. In the trans-Br, O-[Cu(Br)(Hte1P)]center dot H2O species, the central metal ion is surrounded by four in plane nitrogen atoms, one oxygen atom of the pendant moiety in the apical position and a bromide anion positioned trans to the oxygen atom, forming a distorted octahedral coordination sphere. In the compound [Cu(H2te1P)][Cu(Hte1P)]Br3 center dot 6H(2)O, obtained from a highly acidic solution, the bromide anions are placed further away from the copper( II) ion and the coordination environment (N4O) is thus square-pyramidal. In both structures, the protons are associated with non-coordinated phosphonate oxygen atoms.
机译：合成了新的配体，[（1,4,8,11-四氮杂环四癸癸-1-基）甲基]膦酸（H（2）te1P，H2L），并通过电位法研究了其对所选金属离子的络合性能。所述配体与铜（II）形成非常稳定的络合物（log beta（CuL）= 27.34），对其他金属离子的结合具有高选择性（log log（ZnL）= 21.03）。确定了游离配体（以溴化物作为抗衡离子的质子化形式）和两种铜（Ⅱ）配合物（通过在各种pH下结晶获得）的晶体结构。游离配体对这类大环采用常见构象，质子化的氮原子位于虚拟矩形的角中。在反式Br，O- [Cu（Br）（Hte1P）]中心点H2O物种中，中心金属离子被四个平面氮原子，一个悬垂部分的氧原子在顶端位置和一个溴化物阴离子包围位于氧原子的反位，形成扭曲的八面体配位球。在从强酸溶液中获得的化合物[Cu（H2te1P）] [Cu（Hte1P）] Br3中心点6H（2）O中，溴化物阴离子与铜（II）离子和配位环境的距离更远（因此，N 4 O是方形锥体。在两个结构中，质子均与非配位的膦酸酯氧原子缔合。

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