Influencing the Stability of Diaminomethane-Containing Azacrown Ether Ligands in the Presence of Transition-Metal Ions
Influencing the Stability of Diaminomethane-Containing Azacrown Ether Ligands in the Presence of Transition-Metal Ions
复制标题
DOI：
10.1002/ejic.201201564
复制
发表时间：
2013-06-01
影响因子：
2.3
通讯作者：
Batten, Stuart R.
中科院分区：
文献类型：
--
作者：
Gee, William J.;Batten, Stuart R.
新的氮杂冠醚配体双{[3-（吡啶-4-基）-1H-吡唑-1-基]甲基}二氮杂-18-冠-6（b3 pd）（其含有通过二氨基甲烷连接基连接的对吡啶基吡唑侧臂）的评价鉴定了在过渡金属离子存在下经历逆曼尼希断裂的趋势。然而，在与过渡金属离子络合之前用高氯酸钾或碘化钾处理b3 pd赋予了抗碎裂性，使得几周后从浓缩溶液中结晶配位聚合物是可能的。通过对四种含Kb 3 pd的固态结构的研究，得到了四种含Kb 3 pd的固态结构：高氯酸盐（1）、二价锰一维配位聚合物[Mn（Kb 3 pd）（DMF）4]中心点2ClO 4中心点I3（2，DMF = N，N-二甲基甲酰胺）、亚铜二维配位网络[Cu 2（Kb 3 pd）2（I3）（I）3]中心点3 H2O（3）和亚铜一维配位聚合物[Cu（Kb 3 pd）（I）2]（4）。此外，通过原位FTIR光谱、质谱、晶体学和通过分离由部分断裂配体单{[3-（吡啶-4-基）-1H-吡唑-1-基]甲基}二氮杂-18-冠-6（m3 pd）连接的钴络合物来研究逆Mannich过程。配合物的组成为[CoCl_3（Hm_3pd）]中心点H_2O（5）。
The evaluation of a new azacrown ether ligand bis{[3-(pyridin-4-yl)-1H-pyrazol-1-yl]methyl}diaza-18-crown-6 (b3pd), which contains pendant p-pyridylpyrazole arms connected by diaminomethane linkers, identified a tendency to undergo retro-Mannich fragmentation in the presence of transition-metal ions. However, treatment of b3pd with potassium perchlorate or potassium iodide prior to complexation with transition-metal ions imparted a resistance to fragmentation, such that crystallisation of coordination polymers from concentrated solutions after several weeks was possible. Four solid-state structures containing Kb3pd were isolated: a perchlorate salt (1), a divalent manganese 1D coordination polymer [Mn(Kb3pd)(DMF)4]center dot 2ClO4 center dot I3 (2, DMF = N,N-dimethylformamide), a cuprous 2D coordination network [Cu2(Kb3pd)2(I3)(I)3]center dot 3H2O (3) and a cuprous 1D coordination polymer [Cu(Kb3pd)(I)2] (4). Additionally, the retro-Mannich process was investigated by in situ FTIR spectroscopy, mass spectrometry, crystallography and by the isolation of a cobalt complex ligated by a partially fragmented ligand, mono{[3-(pyridin-4-yl)-1H-pyrazol-1-yl]methyl}diaza-18-crown-6 (m3pd). The composition of the cobalt complex was found to be [CoCl3(Hm3pd)]center dot H2O (5).