Metal-Ion Induced In Situ Ligand Oxidation for Self-Assembled Clusters: from Bis(5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl)methane to Alcohol or Ketone.
Metal-Ion Induced In Situ Ligand Oxidation for Self-Assembled Clusters: from Bis(5-(2-pyridine-2-yl)-1,2,4-triazole-3-yl)methane to Alcohol or Ketone.
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DOI：
10.1002/asia.201700719
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发表时间：
2017-09
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通讯作者：
Wei-Quan Lin;Yuan-Yuan Peng-Yuan;L. Tong;J. Jia;Jun‐Liang Liu;Yan‐Cong Chen;Wen-Bin Chen;M. Tong
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文献类型：
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作者：
Wei-Quan Lin;Yuan-Yuan Peng-Yuan;L. Tong;J. Jia;Jun‐Liang Liu;Yan‐Cong Chen;Wen-Bin Chen;M. Tong
金属硝酸盐与配体二（5-（吡啶-2-基）-1，2，4-三唑-3-基）甲烷（H2 L1）的水热反应生成了三种簇合物{Cr2 }、{Zn 12}和{Fe 8}。在金属环{Zn 12}中，H2 L1的亚甲基被原位氧化为羟甲基化的（L2 -O）3-，在螺型{Fe 8}中，H2 L1的亚甲基被原位氧化为刚性的羰基化的（L3 =O）2-。根据对比实验结果，推测NO3-在配体氧化反应中起催化作用。在自组装过程中，金属离子可以被看作是一种“诱导”的工具。
Hydrothermal reactions of metal nitrates and ligand bis(5-(pyridine-2-yl)-1,2,4-triazol-3-yl)methane (H2 L1 ) gave three cluster compounds, {Cr2 }, {Zn12 } and {Fe8 }. Notably, methylene group of H2 L1 was in situ oxidized either to hydroxymethylated (L2 -O)3- in the metallo-ring {Zn12 } or to a rigid carbonylated (L3 =O)2- in the screw-type {Fe8 }. In light of comparative experimental results, NO3- was deduced to be of a catalytic role in the ligand oxidation. Metal ion could be regarded as an "induced" tool for clusters generation in self-assembly process.