三元配合物Ho(Et_2dtc)_3(phen)的合成及其热化学性质  

Synthesis and Thermochemical Properties of the Ternary Complex Ho(Et_2dtc)_3(phen)

作　　者：朱丽[1] 焦宝娟[1] 帅琪[1] 杨旭武[1] 高胜利[1] 史启祯[1] 

机构地区：[1]西北大学化学系

出　　处：《有机化学》2004年第11期1417-1422,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金 (No.2 0 1 71 0 36);陕西省教育厅专项基金 (No.0 1JK2 2 9);西北大学重点基金 (No.0 2NW0 2 )资助项目

摘　　要：改进文献方法 ,以铜试剂 (NaEt2 dtc·3H2 O)和邻菲咯啉 (o phen·H2 O)与低水合氯化钬 (HoCl3 ·3 5 8H2 O)在无水乙醇中反应 ,制得三元固态配合物 .化学分析和元素分析确定该配合物的组成为Ho(Et2 dtc) 3 (phen) .IR光谱表明配合物中Ho3 + 与3个NaEt2 dtc中的 6个硫原子双齿配位 ,同时与o phen中的 2个氮原子双齿配位 ,可推测其配位数为 8.用微量热量计测定了 2 98 15K下液相生成反应的焓变ΔrH m(l) ,为 ( -14 697± 0 0 3 76)kJ·mol-1,通过合理的热化学循环计算了固相生成反应焓变ΔrH m(s) ,为 ( 117 5 0 4± 0 619)kJ·mol-1;改变反应温度 ,研究了配合物的液相生成反应的热力学性质 .配合物的恒容燃烧能ΔcU用精密转动弹热量计测定为 ( -18687 64± 8.2 2 )kJ·mol-1,其标准燃烧焓ΔcH m 和标准生成焓ΔfH m 经计算分别为 ( -1870 6 85± 8 2 2 )和 ( -70 0 1± 9 3 7)kJ·mol-1.The ternary solid complex has been synthesized with sodium diethyldithiocarbamate (NaEt(2)dtc), 1,10-phenanthroline (o-phen) and low hydrated holmium chloride in absolute ethanol by the improvement of the methods reported in reference. The title complex was identified as the general formula of Ho(Et(2)dtc)(3)(phen) by chemical and elemental analyses. IR spectrum of the complex showed that the Ho3+ is coordinated with six sulfur atoms of three NaEt(2)dtc and two nitrogen atoms of phen. It was assumed that the coordination number of Ho3+ is eight. The enthalpy change of liquid-phase reaction [Delta(r)H(m)(circle minus)(l)] was determined as (-14.697 +/- 0.0376) kJ(.)mol(-1) at 298.15 K by a microcalorimeter, and the enthalpy change of the solid-phase reaction [Delta(r)H(m)(circle minus)(s)] was calculated as (117.504 +/- 0.619) kJ(.)mol(-1) on the basis of a thermochemical cycle. The thermokinetics of formation reaction was studied at different temperature by liquid-phase reaction. The constant-volume combustion energy of the complex, Delta(c)U, was determined as (-18687.64 +/- 8.22) kJ(.)mol(-1) by a precise rotating-bomb calorimeter at 298.15 K. Its standard combustion enthalpy, Delta(c)H(m)(circle minus), and standard enthalpy of formation, Delta(f)H(m)(circle minus), were calculated as (-18706.85 +/- 8.22) and (-70.01 +/- 9.37) kJ(.)mol(-1), respectively.

关 键 词：钬配合物 合成 热化学性质 邻菲咯啉 低水合氯化钬 恒容燃烧能 标准燃烧焓 标准生成焓 

分 类 号：O641.4[理学—物理化学]