磷酸二甲酯稀土配合物的合成与红外光谱研究

SYNTHESES AND INFRARED SPECTRA OF RARE EARTH COMPLEXES WITH DIMETHYL PHOSPHATE

本文用稀土氯化物与磷酸三甲酯反应制备了一系列标题配合物RE(DMP)_3(RE=Sm,Eu,Ho,Yb,Lu)。配合物的热分解是一步完成的,由残渣的红外光谱确认其热分解产物为稀土偏磷酸盐。测定了配合物的红外光谱,对其主要吸收谱带进行了归属。红外光谱表明标题配合物与Sm(DMP)_3单晶应具有相同的结构类型,每个稀土原子通过双“O—P—O”桥与邻近的三个稀土原子连接,形成“双桥二十四元环”的环会环的网络结构。RE—O键基本上是离子键。

The solid complexes of Sm, Eu, Ho, Yb and Lu with dimethyl phosphate (DMP) weresynthesized by reaction of trimethyl phosphate(TMP) with corresponding rare earth chlorides. The mechanism of thermodecomposition of the complexes has been studied. Their infraredspectra were measured and main infrared absorption bands were assigned. The result showedthat the polymeric title complexes are extremely similar to Sm(DMP)_3 single crystal in thespectral properties of RE-O bond and PO_2 group. Thus these complexes may have the samemolecular configuration, i.e. dimetbyl phosphate anions coordinate with lanthanide atomsthrough double O-P-O bridges to form a special network of rings-linking-rings, each ofwhich consists of twenty-four atoms. The RE-O bond of RE(DMP)_3 is principally ionic.