主族(S,Se,Te)三鐵羰基化合物與含第十一、十二族金屬(Cu,Ag,Cd,Hg)及含磷、碳烯試劑之反應與化性和物性探討

Abstract

利用[EFe3(CO)9]2─ (E = S, Se, Te) 與 [Cu(MeCN)4][BF4] 和一當量dppm於THF或是CH2Cl2及冰浴下反應，可得一系列不同溶劑配位雙銅含磷化合物 [EFe3(CO)9Cu2(dppm)(THF)]、[EFe3(CO)9Cu2(dppm)(MeCN)] (E = S, Se, Te)。將此具有溶劑配位之化合物用去離子水長時間充分清洗，則會獲得脫去其配位溶劑，形成雙銅含磷化合物 [EFe3(CO)9Cu2(dppm)] (E = S, Se, Te)。若將反應之dppm提高為兩當量時，可於低溫得到雙銅含磷雙橋接並具有溶劑配位化合物 [EFe3(CO)9Cu2(dppm)2(MeCN)] (E = S, Se)。而高溫反應可得雙銅含磷雙橋接無溶劑配位化合物 [EFe3(CO)8Cu2(dppm)] (E = S, Se, Te)。此外，一系列化合物具有轉換關係，亦藉由理論計算探討。

When [EFe3(CO)9]2─ (E = S, Se, Te) were treated with [Cu(MeCN)4][BF4] and dppm in the molar ratio of 1:2:1 in THF or CH2Cl2 in an ice-water bath, a series of solvent-coordinated complexes, [EFe3(CO)9Cu2(dppm)(THF)], and [EFe3(CO)9Cu2(dppm)(MeCN)] (E = S, Se, Te), were obtained. When these resultant complexes were further stirred in water for a long time, the coordinated solvent could be removed to form [EFe3(CO)9Cu2(dppm)] (E = S, Se, Te). Moreover, when the reactions were carried out in the molar ratio of 1:2:2 at –30 oC, [EFe3(CO)9Cu2(dppm)2(MeCN)] (E = S, Se) were obtained. However, when similar reactions were carried out at 40 oC, [EFe3(CO)8Cu2(dppm)] (E = S, Se, Te) were obtained. Furthermore, the nature and transformation of the resultant complexes were discussed and elucidated by DFT calculations.