二氯合铜(Ⅰ)酸四(三苯基氧膦)二氯合希土(Ⅲ)配合物的合成和红外光谱研究  

SYNTHESIS AND INFRARED STUDIES OF TETRAKIS(TRIPHENYLPHOSPHINE OXIDE)DICHLOROCUPROSDICHLOROLANTHANIDES

作　　者：张明杰[1] 王序昆[2] 荆煦瑛 王积涛[2] 

机构地区：[1]北京大学化学系希土中心 [2]南开大学元素有机化学研究所,天津300071

出　　处：《无机化学学报》1990年第4期377-380,共4页Chinese Journal of Inorganic Chemistry

摘　　要：合成了通式为[(Ph_3P=O)_4LnCl_2][CuCl_2](Ln=La、Ce、Pr、Nd、Sm、Eu、Gd、Tb、Dy、He、Er、Y)的新配合物共12个,测定了它们的红外光谱(100～4600m^(-1))和部分配合物的^(31)P NMR.比较了[(Ph_3P=O)_4LnCl_3]、[(Ph_3P=O)_4LnCl_2]^+和[(Ph_3P=O)_5LnCl]^(2+)的P=O伸缩振动频率.结果表明希土配合物的正电荷越高,P=O基对希土离子配合能力越强,P=O伸缩振动频率更多地移向低波数,ν_(P=O)的顺序为:[(Ph_3P=O)_4LnCl_3]>[(Ph_3P=O)_4LnCl_2]^+≥[(Ph_3P=O)_5LnCl]^(2+).讨论了希土配位键的共价性。A series of new complexes with the general formula of [(Ph3P = O4LnCl]2[CuCl2] (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er. and Y) has been prepared and characterized. The 31P NMR showed a chemical shift for coordinated Ph3P = O at 37.0 ppm in lower field compared to the chemical shift for free Ph3P = O The vp = o in IR of these complexes were compared with those for (Ph,P = O)4LnCl,. [(Ph,P=O)4LnCl2]+ and [(Ph3P=O),I.nCl]2+. It was observed that the more the positive charge was on the lanthanidc complex, the stronger the coordination of P = O group to lanthanidc was, and the vp = 0 moved to lower wave number. The vp=0 for these complexes were arranged in the following order: (Ph3P = O)4LnCl3>[(Ph3P = O)4LnCI2]>[(Ph3P = O)5LnCl]2+ It was observed also that the Ln-Cl stretching frequency appeared at 230-241cm-1 (for Ln = La-Er) and at 265cm-1 (for Y) and the Cu-Cl stretching and distortion frequencies appeared at 409-412 and 108-114cm-1, respectively.

关 键 词：稀土配合物 铜 三苯基氧化膦 合成 

分 类 号：O614.33[理学—无机化学]