双核有机锡(Ⅳ)配合物[Ph_3Sn(CH_3OH)O_2CC_6H_4CO_2(CH_3OH)-SnPh_3]·2CH_3OH和[Ph_3SnS_2CN(CH_2CH_2)_2NCS_2SnPh_3]·2CH_3OH的合成、表征和晶体结构

利用三苯基氯化锡和对苯二甲酸二钠、哌嗪荒酸二钠在甲醇中反应 ,合成了双核有机锡 (Ⅳ )配合物 [Ph3 Sn (CH3 OH)O2 CC6H4 CO2 (CH3 OH)SnPh3 ]·2CH3 OH (1)和 [Ph3 SnS2 CN(CH2 CH2 ) 2 NCS2 SnPh3 ]·2CH3 OH (2 ) .通过元素分析、红外光谱和核磁共振氢谱对其结构进行了表征 .用X射线单晶衍射测定了这两个化合物的晶体结构 .化合物 1为单斜晶系 ,空间群P2 1/n ,a =1.5 199(5 )nm ,b =0 .90 0 0 (3)nm ,c =1.82 0 6 (6 )nm ,β =113.970 (5 )° ,Z =2 ,V =2 .2 75 5(13)nm3 ,Dc=1.413g/cm3 ,μ =1.146mm-1,F(0 0 0 ) =980 ,R1=0 .0 35 3,wR2 =0 .0 6 0 6 .化合物 2为单斜晶系 ,空间群P2 1/c,a =1.5 0 6 6 (5 )nm ,b =1.0 875 (4 )nm ,c =1.35 42 (5 )nm ,β =91.6 14(5 )°,Z =2 ,V =2 .2 178(14)nm3 ,Dc=1.498g/cm3 ,μ =1.35 1mm-1,F(0 0 0 ) =10 0 8,R1=0 .0 40 1,wR2 =0 .1148.在 1和 2的晶体中 ,锡原子呈五配位畸变三角双锥构型 .配合物

以双核有机锡(Ⅳ)配合物为中性载体高选择性硫氰酸根电极的研究

研究了双核三苄基甲醇锡（Ⅳ）哌嗪荒酸酯配合物[Sn（Ⅳ）-BTMTP]为中性载体的PVC膜阴离子选择性电极。这类电极对硫氰酸根离子呈现出优良的电位响应性能和选择性,并呈现出反Hofmeister选择性行为。其选择性序列为：SCN-〉I-〉ClO4-〉NO2-〉NO3-〉Cl-〉SO42-〉AC-,该电极在pH=4.0的磷酸盐缓冲体系中对SCN-呈超能斯特响应,响应范围为1.0×10-1~3.2×10-5 mol/L,斜率为-72.4 mV/dec,检出限为1.28×10-5mol/L。采用交流阻抗及紫外光谱研究了阴离子与载体的作用机理。将该电极用于废水分析,结果令人满意。

Synthesis and Molecular Structure of Binuclear Organotin Complex Bridged by Piperazinylbidithiocarbamate Anion

The title complex bistri(o-fluorbenzyl)tinpiperazinylbisdithiocarbamate (C48H44- F6N2S4Sn2, Mr = 1128.47) was synthesized by the reaction of tri(o-fluorbenzyl)tin chloride with piperazinylbisdithiocarbamate in 2:1 molar ratio. The structure was characterized by elemental analysis, IR and 1H NMR, and the crystal structure was determined by X-ray single-crystal diffrac- tion. The crystal belongs to triclinic, space group P with a= 10.348(5), b = 10.636(6), c = 13.279(7) , a = 68.445(9), b = 86.763(9), g = 61.278(8)o, Z = 1, V = 1179(1) 3, Dc = 1.589 g/cm3, m = 1.296 mm-1, F(000) = 564, R = 0.0534 and wR = 0.0849. In the complex, the tin atoms are five-coordinate to a distorted tirgonal bipyramidal configuration.