室溫中將E(E = Se, Te)、Cr(CO)6和Fe(CO)5在高濃度的KOH甲醇溶液中產生了雙三角錐結構[PPN]2[E2Cr2Fe(CO)10](E = Se, Te);若Se、Cr(CO)6和Fe(CO)5在高濃度的NaOH甲醇溶液中則會產生八面體結構的[PPN]2[Se2Cr2Fe2(CO)12]。 將莫耳數比1:1.5:1的E(E = Se, Te)、Mo(CO)6和Fe(CO)5在KOH / MeOH溶液中加熱迴流後,可產生八面體結構的[PPh4]2[E2Mo2Fe2(CO)12](E = Se, Te);在Se系統中,若以相同比例在NaOH / MeOH中反應,除了[PPh4]2[Se2Mo2Fe2(CO)12]之外,還可得[PPh4]2[Se2MoFe3(CO)11];將E的來源改為EO32-(E = Se, Te),在Se系統會先產生[PPh4]2[Se2Mo2Fe2(CO)12],而Te系統須較久的時間才會形成[PPh4]2[Te2Mo2Fe2(CO)12],隨著反應時間的增加,兩系統均會發現有未知的綠色產物出現。 本研究提供一個新的合成方式來合成混合過渡金屬團簇化合物,且成功的得到一系列陰離子的化合物,並有個不錯的方法可以將所得的產物單離出來,使我們對如何合成混合過渡金屬團簇化合物深具信心。
The reaction of E(E = Se, Te)with Cr(CO)6、Fe(CO)5 in highly concentrated KOH / MeOH solution at room temperature produces the trigonal bipyramidal cluster compounds [PPN]2[E2Cr2Fe(CO)10] ( E = Se, Te). On the other hand, Se reacts with Cr(CO)6、Fe(CO)5 in highly concentrated NaOH / MeOH solution gives the new compound [PPN]2[Se2Cr2Fe2(CO)12], which displays an octahedral core geometry. Reaction of E ( E = Se, Te) with Mo(CO)6、Fe(CO)5 in KOH / MeOH solution at 70 oC produces the octahedral cluster compounds [PPh4]2[E2Mo2Fe2(CO)12] (E = Se, Te). In the Se system, using NaOH / MeOH under the similar conditions, we obtain the octahedral compound [PPh4]2[Se2Mo2Fe2(CO)12] and another new octahedral product [PPh4]2[Se2MoFe3(CO)11] . Utilizing EO32- instead of E powder(E = Se, Te), we obtain the same E2Mo2Fe2 (E = Se, Te) octahedral clusters from the reactions with Mo(CO)6 and Fe(CO)5. In the case of SeO32-, the reaction requires a milder condition; however, in the case of TeO32-, the reaction needs prolonged heating, both with the formation of unknown green compounds. In summary, a new synthesis and isolation of group 16 (E = Se, Te) containing mixed transition metal carbonyl clusters is developed. Further extension to other mixed metal system is promising.