Co[(C_(2)H_(5)O)_(2)PS_(2)]_(3)·1/2H_(2)O的合成和分子结构

Synthesis and Crystal Structure of Tri-(O,O’ -Diethyldithiophosphato) Cobalt(Ⅲ)

用光谱法研究了双-(O,O’-二硫代磷酸酯)合钴(Ⅱ)的氧化过程。用电子光谱、光电子能谱、差热-热重分析和质谱等对氧化产物进行了表征。并用X射线衍射法测定了晶体结构。晶体属三斜晶系,空间群为P1-,晶胞参数为:α=9.805(1)■,b=9.812(2)■,c=14.271(2)■,α=89.46(2)°,β=89.42(1)°,γ=86.95(2)°,V=1370.9■,Z=2,Dc=1.509 g·cm^(-3),F(000)=645 e。Co(Ⅲ)与三个二硫代磷酸酯形成六配位的八面体配合物。

Oxidation process of CoC(C_(2)H_(5)O)_(2)PS_(2)]_(2) was studied by UV-Vis method to get the title compound. The rate of oxidation reaction is very slow and seems depending on alkyl group in the ligand molecule. The oxidation product CoC(C_(2)H_(5)O)_(2)PS_(2)]3·1/2 H_(2)O was characterized by UV-Vis, MS, TG-DT and PES.The crystal of CoC(C2H5O)2PS2]3 · 1/2 H_(2)O belongs to Iriclinic, space group P1, parameters of unit cell are:α= 8.805(1)■, b=9.812(2)■, c = 14.271(2)■, α = 89.46(2)°, β=89.42(1)°, γ=86.95(2)°,V=1370.9■^(3), Z=2, Dc = 1.509g·cm^(-3), F(000) = 645e, final R= 0.080 for 4279 reflections with I≥3σ(Ⅰ) bond lengths of Co-S are 2.319 + 0.004A. Bond angles of cobalt atom and two sulphur atoms in the same dithiophosphate group are 85.07-85.35°. Bond angles of cobalt atom and any two neighbour sulphur atoms which are not in same dithiophosphate group are 89.35 - 95.35 °.There have three oxygen atoms of crystal water with 1/6 possibility for each in unsymmetry unit. Nonbonding distances between these oxygen and sulphur atoms are 2.12-2,27A, which are much less than the sum of the van der Waals radii. It shows that some kinds of hydrogen bonds such as O-H...S are present.