光谱法研究Ni[(C_4H_9O)_2PS_2]_2与氮碱的加合反应(Ⅱ)

Study on Adductive Reaction of Ni[(C_4H_9O)_2PS_2]_2 with Nitrogen Base by Spectrophotometric Method(Ⅱ)

用光谱法研究了NiL2 在 30℃时与乙胺、正丙胺、正丁胺和正戊胺在乙醇溶液中的加合反应。伯胺类氮碱 (B)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。实验测定了反应的平衡常数lgβn 及加合分子数n。lgβn 随胺类碱度 pKa值增加而增大 ,且可以经验公式来描述lgβ1 =- 9 6 9+1 15pKa ;lgβ2 =- 18 73+2 2

Reaction of Ni[(C 4H 9O) 2PS 2] 2 with ethylamine, n propylamine, n butylamine, and n amylamine have been studied by spectrophotometry in ethanol at 30℃ For nitrogen base(B), the adduct formation of NiL 2·B and NiL 2·B 2 is established, and their additive equilibrium constants ( lg β n) and molecular number (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 constants ( lg β n) increase with basicity (pKa ) of nitrogen base and can be described by experimental formulas: lg β 1 = -9 69 + 1 15 pKa; lg β 2 = -18 73 + 2 28 pKa