【摘要】 用光谱法研究了Ni[(C4 H9O) 2 PS2 ]2 (NiL2 )与吡啶、4 甲基吡啶、3,5 二甲基吡啶、2 ,4 二甲基吡啶和 2 ,4,6 三甲基吡啶 ,温度为 32℃时在乙醇溶剂中的加合反应。B(2 ,4 二甲基吡啶和 2 ,4,6 三甲基吡啶 )只能与NiL2 生成一种 1∶2的六配位加合物NiL2 ·B2 ,其他氮碱与NiL2 生成 1∶1的五配位NiL2 ·B和 1∶2的六配位NiL2 ·B2 两种加合物。所有五配位NiL2 ·B和六配位NiL2 ·B2 加合物的吸收光谱分别由NiNS4 和NiN2 S4 发色基团所产生。实验测定了加合反应的平衡常数lgβn 和加合反应分子数n ,lgβn 随氮碱分子碱度pka增加而增大 ,且可以用经验公式来描述 :lgβ1=- 0 186 +0 35 2pKa ;lgβ2 =3 16 +0 0 83pKa更多还原

【Abstract】 Reactions of Ni[(C 4H 9O) 2PS 2] 2 (NiL 2) with Pyridine, 4 methylpyridine, 3,5 lutidine, 2,4 lutidine and 2,4,6 lutidine have been studied by spectrophotometry in ethanol at 32℃. With B =2,4 lutidine and 2,4,6 lutidine, the formation of NiL 2·B 2 only is concluded. For other nitrogen bases(B), the adduct formation of NiL 2·B and NiL 2·B 2 is established, and their adductive equilibrium constants (lg β n ) and molecules (n) have been discussed. All the NiL 2·B and NiL 2·B 2 complexes exhibit virtually the same electronic spectra arising from the five coordinate NiNS 4 and six coordinate NiN 2S 4 chromophore respectively. The adductive equilibrium constants (lg β n ) increase with basicity (pKa ) of nitrogen bases and can be described by experimental formulas: lg β 1 =-0 186+ 0 352 pKa;lg β 2 =3 16+0 083 pKa.更多还原