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

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。

SYNTHESIS AND INFRARED STUDIES OF TETRAKIS(TRIPHENYLPHOSPHINE OXIDE)DICHLOROCUPROSDICHLOROLANTHANIDES

A series of new complexes with the general formula of (Ph3P = O4LnCl]2CuCl2] (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.