二茂铁基β-二酮及其Cu(Ⅱ)、Ni(Ⅱ)配合物的燃速催化性质  

Burning-Rate Catalytic Properties of Ferrocenyl β-Diketones and Their Cu(Ⅱ),Ni(Ⅱ) Complexes

作　　者：朱学友[1] 李小红[1] 韩凤娇[1] 张世晨[1] 赵海英[1] 边占喜[1] 

机构地区：[1]内蒙古自治区精细有机合成重点实验室,内蒙古大学化学化工学院,呼和浩特010021

出　　处：《有机化学》2015年第4期922-926,共5页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21102068);内蒙古自治区高等学校科学研究(No.NJZZ001);内蒙古自治区自然科学基金(Nos.2013MS0207,2014JQ02)资助项目~~

摘　　要：合成了含有苯基的二茂铁β-二酮,并对其结构进行了表征.在核磁共振氢谱中,苯环上含有拉电子的硝基时,β-二酮烯醇式含量几乎是100%,而含有给电子的甲氧基时,其烯醇异构体含量下降到84%.当将其与Cu（II）或Ni（II）配位后,在紫外吸收光谱中,300 nm以下归属于Fe（d）-π＊和芳基π-π＊的跃迁向长波方向移动5~17 nm.热重-差示扫描量热法（TG-DSC）实验表明,添加二茂铁基β-二酮或它们的Cu（II）或Ni（II）配合物于高氯酸铵（AP）中,不仅在一定程度上抑制了AP高温热降解阶段的升华,而且可使AP的热降解温度提前,以Cu（II）配合物提前得更为显著,含有甲氧基的Cu（II）配合物可使AP的热降解温度提前87℃.因此相对于二茂铁β-二酮配体及Ni（II）配合物,Cu（II）配合物是更好的燃速催化剂.Ferrocenyl fl-diketones containing benzene ring have been synthesized and characterized. The content of enol iso- mer is almost 100% in fl-diketone containing nitro group, and decreases to 84% in that containing methoxy group in CDCI3 from 1H NMR. When they were converted to the Cu（II） or Ni（II） complexes, the stretching bands of C=O and C=C in enol isomers shifted 57～69 and 10～27 cm^-1 to low wave number, respectively. The absorption bands below 300 nm assignabling to Fe（d）-π＊ and π-π＊ electronic transitions of the aromatic rings in UV-vis absorption spectra shifted bathoehromically 5～ 17 nm. The thermogravimetry-differential scanning calorimetry （TG-DSC） measurements confirmed that not only the sublimation for ammonium perchlorate （AP） on the high-temperature decomposition stage was inhabited but also the obvious catalytic effect on the decomposition of AP was found after adding these ferrocenyl β-diketones or their Cu or Ni complexes to AP, and the Cu complexes had the most significant effect. The Cu complex containing methoxy group decreased the decomposition temperature of AP by 87 ℃. So the Cu complexes are more effective catalysts than ferrocenyl β-diketone ligands and the Ni complexes.

关 键 词：二茂铁 Β-二酮 过渡金属配合物 高氯酸铵 燃速催化 

分 类 号：O643.32[理学—物理化学]