【摘要】 利用相转移试剂四庚基溴化铵将含过渡金属单空位Ｋｅｇｇｉｎ结构杂多化合物［ＸＷ１１Ｏ３９Ｚ（Ｈ２Ｏ）］ｎ－（Ｘ＝Ｃｒ，Ｍｎ，Ｆｅ；Ｚ＝Ｃｏ，Ｚｎ，Ｃｒ；ｎ＝６，７），从水相转移至非极性溶剂有机相苯中．并根据电子光谱、ＩＲ谱、ＥＳＲ谱的变化，进一步考察了它们在有机相苯中的配位水脱去，形成配位不饱和杂多阴离子的情况，同时详细研究了该类杂多阴离子所含表面配位水与若干无机阴离子及有机配体的取代反应．实验表明，杂多阴离子由水相转移至有机相苯后，较易脱去配位水形成溶剂配位不饱和离子．当加入Ｌｅｗｉｓ碱时，可迅速恢复饱和配位．ＥＳＲ测定给出某些含过渡金属单空位Ｋｅｇｇｉｎ结构杂多阴离子相转移前后价态变化及电子转移情况．更多还原

【Abstract】 Heteropoly compounds with lacunary Keggin structure containing transition metals [XW 11 O 39 Z(H 2O)] n- (X=Cr, Mn, Fe; Z=Co, Zn, Cr; n =6,7) have been transferred from aqueous solutions into non polar solvent (benzene) with the aid of transfer agent (tetraheptylammonium bromide). Based on electronic spectra,IR and ESR, the above compounds can become unsaturated coordination heteropolyanions through dehydration reaction in benzene and the coordination water can occur replacement reaction with many inorganic anions and organic ligands. Experimental results show that after phase transfer, the heteropolyanions are ease to remove their coordination water molecules and become unsaturated coordination anions. But they can rapidly restore their saturated structure when Lewis bases are added. ESR determinations have given the valence change and electron transfer for some heteropoly compounds with lacunary Keggin structure containing transition metals.更多还原