含主族元素 (S、Se、Te) 與過渡金屬 (Cr、Mn、Fe、Ru) 團簇化合物的合成及其反應性探討

Abstract

1. Te─Fe─Cu─X 化合物之合成 利用 [TeFe3(CO)9]2− 在 THF 溶液環境下與一當量 CuX (X = Cl、Br、I) 於冰浴中反應，可生成錯合物 [TeFe3(CO)9CuX]2− (X = Cl、Br、I)。將主體與引入的 CuX 當量數比例改為 1：2~3 在 THF 或 CH3CN 於冰浴中反應，會生成錯合物 [TeFe3(CO)9Cu2X2]2− (X = Cl、Br、I)。另一方面，團簇物 [TeFe3(CO)9CuX]2− (X = Cl、Br、I) 可與一當量的 [Cu(CH3CN)4]BF4 試劑反應，擴核形成結構 [{TeFe3(CO)9}2Cu3X]2− (X = Cl、Br、I)。[TeFe3(CO)9Cu2X2]2− (X = Cl、Br) 若是與一當量 [Cu(CH3CN)4]BF4 反應，則可形成穩定結構 [{TeFe3(CO)9}2Cu4X2]2− (X = Cl、Br)。

2. E─Ru─Cr─Cu (E = S、Se) 化合物之合成 將 Ru3(CO)12、Cr(CO)6 與 E (E = S、Se powder) 以 Ru : Cr : E 的原子比例為 1：2：2 於 ~ 4 M KOH 之 MeOH 環境下加熱，將生成團簇物 [E2Ru3Cr(CO)10]2− (E = S、Se)。錯合物 [S2Ru3Cr(CO)10]2− 可與一當量的 [Cu(CH3CN)4]BF4 於低溫下反應，耦合形成 [{S2Ru3Cr(CO)10}2(CuNCCH3)2]2−。上述三種團簇物結構中有罕見 Ru─Cr 鍵，並且均具有缺電子的特性。

3. E─Mn (E = S、Te) 化合物之合成 將 Mn2(CO)10 與 S powder 以 Mn : S 的原子比例為 4：10 於 4 M KOH 之 MeOH 溶液環境下反應，將生成巨大的團簇物 [S10Mn6(CO)18]4−。如果使用 Te powder，以 Mn：Te 的原子比例為 9：10 於 ~ 1 M KOH 之 MeOH 中於低溫下反應，則會生成錯合物 [Te3Mn2(CO)8]2−。前者的結構具有豐富的轉換特性，後者結構則具有良好的反應性可作為起始物用以開發新結構。

4. S─Mn─Cr 化合物之合成 [S2Mn3(CO)9]− 在 4 M KOH 的 MeOH 溶液中與一當量 Cr(CO)6 於室溫下反應，可生成團簇物 [HS2Mn3Cr(CO)14]−。若改變反應比例與兩當量的 Cr(CO)6 反應，將生成團簇物 [HS2Mn3Cr2(CO)19]−。錯合物 [HS2Mn3Cr(CO)14]− 可藉外加一當量的 Cr(CO)6，於 CH2Cl2 溶液中加熱轉換成 [HS2Mn3Cr2(CO)19]−。

針對上述一系列新開發出的結構，其反應機構、物性、化性及電化學的性質分析，我們利用密度泛函數理論 (Density Functional Theory) 進行分子模擬並以 B3LYP 層級進行理論計算作為實驗結果的印證。

1. Synthesis of Te─Fe─Cu─X complexs When [TeFe3(CO)9]2− was treated with 1 equiv of CuX in THF in an ice-water bath, clusters [TeFe3(CO)9CuX]2− (X = Cl, Br, I) were formed, respectively. When the reactions were carried out in the molar ratio of 1: 2~3 in THF or CH3CN in an ice-water bath, [TeFe3(CO)9Cu2X2]2− (X = Cl, Br, I) could be obtained. On the other hand, [TeFe3(CO)9CuX]2− (X = Cl, Br, I) could react with 1 equiv of [Cu(CH3CN)4]BF4 to form clusters [{TeFe3(CO)9}2Cu3X]2− (X = Cl, Br, I), respectively. [TeFe3(CO)9Cu2X2]2− (X = Cl, Br) could further react with 1 equiv of [Cu(CH3CN)4]BF4 to form clusters [{TeFe3(CO)9}2Cu4X2]2− (X = Cl, Br), respectively.

2. Synthesis of E─Ru─Cr─Cu (E = S, Se) complexs When Ru3(CO)12 and Cr(CO)6 were treated with E (E = S, Se powder)/KOH (4M) in refluxing MeOH with the atomic ratio of Ru：Cr：E = 1：2：2, clusters [E2Ru3Cr(CO)10]2− (E = S, Se) were formed, respectively. [S2Ru3Cr(CO)10]2− could react with 1 equiv of [Cu(CH3CN)4]BF4 in low temperature to form cluster [{S2Ru3Cr(CO)10}2(CuNCCH3)2]2−. This series of clusters contains rare Ru─Cr bonds and are electron deficient species.

3. Synthesis of E─Mn (E = S, Te) complexs When Mn2(CO)10/KOH (4M) reacted with S powder (atomic ratio of Mn：S = 4：10) in MeOH, large cluster [S10Mn6(CO)18]4− was formed. If Mn2(CO)10 was treated with Te powder/1 M KOH (atomic ratio of Mn：Te = 9：10) in MeOH, complex [Te3Mn2(CO)8]2− was formed. [S10Mn6(CO)18]4− and [Te3Mn2(CO)8]2− are both reactive species and involve in many interesting structural transformations in E─Mn (E = S, Te) systems.

4. Synthesis of S─Mn─Cr complexs When [S2Mn3(CO)9]−/KOH (4M)/MeOH was treated with 1 equiv of Cr(CO)6, [HS2Mn3Cr(CO)14]− was formed. If [S2Mn3(CO)9]−/KOH (4 M)/MeOH was treated with 2 equiv of Cr(CO)6, [HS2Mn3Cr2(CO)19]− was formed. [HS2Mn3Cr(CO)14]− could further react with Cr(CO)6 in CH2Cl2 to form cluster [HS2Mn3Cr2(CO)19]−. In addition, the formation, the nature, and some electrochemistry of this new series of clusters are further understood by molecular calculations at the B3LYP level of the density functional theory.