Iron(III) coordination induced novel 18-metallacrown-6 complex: esterification and isolation of the ligand.
Iron(III) coordination induced novel 18-metallacrown-6 complex: esterification and isolation of the ligand.
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DOI：
10.1039/b814093f
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发表时间：
2009-01
影响因子：
4
通讯作者：
Longfei Jin;Huiyao Yu;Shuxiang Wu;Fengping Xiao
中科院分区：
文献类型：
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作者：
Longfei Jin;Huiyao Yu;Shuxiang Wu;Fengping Xiao
以较高的产率合成了三阴离子七齿配体(Z)-3-(水杨酰肼甲酰基)丙烯酸((Z)-H(4)shcpa)(1)，并与FeCl(3)·6H(2)O反应生成[Fe(III)(6)(C(12)H(9)N(2)O(5))(6)(H(2)O)(2)(CH(3)OH)(4)]x6CH(3)OH(2)。用单晶X射线衍射法对该配合物进行了表征。在自组装过程中，配体被酯化并转移到(Z)-3-(水杨酰肼甲酰基)丙烯酸甲酯((Z)-H(3)mshcp)(3)。在结构中，中性Fe(III)络合物含有一个18元金属冠环，由6个Fe(III)和6个三阴离子配体组成。18元金属冠环是由六个[Fe(III)-N-N]型结构单元串联而成。由于配体对Fe(3+)离子的经向配位作用，配体以交替的Lambda/Delta形式推进Fe(3+)离子的立体化学。用SnCl2对金属冠醚进行处理，可得到纯净酯。此外，我们还用另一种还原剂锌粉得到了还原的酯化配体3-(水杨基肼甲酰基)丙酸甲酯(H3mshcp)(4)。
The trianionic heptadentate ligand, (Z)-3-(salicylhydrazinocarbonyl) propenoic acid ((Z)-H(4)shcpa) (1), has been synthesized in good yield and reacted with FeCl(3).6H(2)O, to produce the complex [Fe(III)(6) (C(12)H(9)N(2)O(5))(6)(H(2)O)(2)(CH(3)OH)(4)] x 6CH(3)OH (2). The complex has been characterized by single-crystal X-ray diffraction. In the self-assembly process the ligand was esterified and transferred into (Z)-methyl 3-(salicylhydrazinocarbonyl) propenoate ((Z)-H(3)mshcp) (3). In the structure, the neutral Fe(III) complex contains a 18-membered metallacrown ring consisting of six Fe(III) and six trianionic ligands. The 18-membered metallacrown ring is formed by the succession of six structural moieties of the type [Fe(III)-N-N]. Due to the meridional coordination of the ligands to the Fe(3+) ions, the ligands enforce the stereochemistry of the Fe(3+) ions as a propeller configuration with alternating Lambda/Delta form. The metallacrown can be treated with SnCl(2) to obtain purified ester. In addition, we have also obtained reduced esterified ligand, methyl 3-(salicylhydrazinocarbonyl) propanoate (H3mshcp) (4) with another reductant Zn powder.