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化学学报
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化学学报 ›› 1994, Vol. 52 ›› Issue (11): 1064-1070. 上一篇    下一篇

研究论文

杂多阴离子的相转移化学 Ⅰ.取代的Keggin及Dawson结构杂多阴离子在非极性溶剂中的溶剂化行为研究

王恩波;刘霞;王作屏;张保建;高丽娟;詹瑞云;刘雅言   

  1. 东北师范大学化学系;中国科学院长春应用化学研究所
  • 发布日期:1994-11-15

Phase transfer chemistry of heteropolyanionsⅠ.Research on solvation behavior of substituted Keggin and Dawson anions in the non-polar solvents

WANG ENBO;LIU XIA;WANG ZUOPING;ZHANG BAOJIAN;GAO LIJUAN;ZHAN RUIYUAN;LIU YAYAN   

  • Published:1994-11-15

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利用四庚基溴化铵将Keggin结构的杂多阴离子ZW~1~1O~3~9M(H~2O)^n^-(Z=Si,Ge,P,M=Ni^2^+,Cu^2^+,Cr^3^+,Co^2^+,n=4～6)和Dawson结构的杂多阴离子P~2W~1~7O~6~1M(H~2O)^n^-(M=Ni^2^+,Cu^2^+,Cr^3^+,Co^2^+,n=7,8) 从水溶液中转移至非极性溶剂(苯或甲苯)中,并观察到在水溶液中难以进行的配位水的脱去反应,形成配位不饱和的杂多阴离子.当加入Lewis碱如丙酮,吡啶等,可迅速恢复饱和配位,其电子吸收光谱也相应变化,基本恢复到配位饱和时的数值,有ESR信号.实验表明,在非极性溶剂中,配体之间相互进行的取代反应,吡啶的配位能力最强, 发生了取代反应ZW~1~1O~3~9M(L)^n^-+Py→ZW~1~1O~3~9M(Py)^n^-+L(L=丙酮,乙腈等).同时我们也研究了温度,杂多阴离子浓度,惰性气体流量对杂多阴离子在非极性溶剂中的溶剂化行为的影响,得到了相转移的一般规律,为杂多阴离子在非极性溶剂中的催化研究提供了理论依据

关键词: 氧化铜, 杂多酸, 氧化硅, 氧化铬, 氧化钴, 氧化镍, 氧化锗, 溶剂化, 氧化磷, 氧化钨

The heteropolyanions of the Keggin structure ZW11O39M(H2O)n- (Z = Si, Ge, P, M = Ni2+, Cu2+, Cr3+, Co2+, n = 4 ~ 6) and Dawson structure P2W17O61M(H2O)n- (M = Ni2+, Cu2+, Cr3+, Co2+, n = 7,8) have been transferred into the non-polar solvents (benzene, toluene), with the aid of tetraheptylammonium bromide. We found that the dehydration reaction, which was difficult to carry out in the aqueous solution, could form coordinatively unsatd. site. When the polar solvent such as acetone, pyridine etc. was added, the anhydrous heteropolyanions could rapidly cover saturated coordination state. Their electronic absorption spectra were similar to each other. The ESR spectra showed activity. In the non-polar solvents, the coordination ability of pyridine is the strongest in the ligand substitution reaction. The substitution reaction was carried out as following: ZW11O39M(L)n- + Py ?ZW11O39M(Py)n-+ L (L = acetone, acetonitrile, etc.). In the mean time, we also studied how the temperature, the concentration of heteropolyanions and flow of inert gas affected the solvation behavior of heteropolyanions in the non-polar solvent. A general rule about phase transfer was concluded from the experiments, which will provide the theor. base of the catalytic research on heteropolyanions in the non-polar solvent.

Key words: COPPER OXIDE, HETEROPOLYACID, SILICON OXIDE, CHROMIUM OXIDE, COBALT OXIDE, NICKEL OXIDE, GERMANIUM OXIDE, SOLVATION, PHOSPHORUS OXIDE, TUNGSTEN OXIDE

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