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利用四庚基溴化铵将Keggin结构的杂多阴离子ZW_(11)O_(39)M(H_2O)~(n-)(Z=Si,Ge,P;M=Ni~(2+),C~(2+),Cr~(3+),Co~(2+);n=4～6)和Dawson结构的杂多阴离子P_2W_(17)O_(61)M(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,吡啶配位能力最强,发生了取代反应ZW_(11)O_(39)M(L)~(n-)+Py→ZW_(11)O_(39)M(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.
The heteropolyanions of the Keggin structure were synthesized using tetraheptylammonium bromide. The complexing anions of ZW 11 O 39 W (H 2 O) ~ (n -) (Z = Si, Ge, P; M = Ni ~ (2 + (17) O_ (61) M (H_2O) ~ (n) ~ (2 +), Cr ~ (3 +) and Co ~ (2 + (M = Ni ~ (2 +), Cu ~ (2 +), Cr ~ (3 +), Co ~ (2 +); n = 7,8) from the aqueous solution to apolar solvents (benzene or toluene ), And observed in the aqueous solution difficult to carry out coordination water de-reaction, the formation of coordination heteroatom anion.When adding Lewis base such as acetone, pyridine, etc., can quickly restore the saturated coordination, the electronic absorption The spectrum also changes accordingly, and the value of ESR signal is basically restored to the value when there is coordination saturation. Experiments show that in non-polar solvents, the substitution reaction between ligands leads to the strongest pyridine coordination ability and the substitution reaction ZW 11 O 39 M L - n + Py → ZW 11 O 39 M Py + n + L (L = acetone, acetonitrile, etc.) At the same time we The effects of temperature, heteropolyanion concentration and inert gas flow rate on the solvating behavior of heteropolyanions in non-polar solvents were also studied. The general law of phase transfer was obtained, and the catalytic activity of heteropolyanions in non-polar solvents Research provides a theory It is.