Main Group (S, Se, or Te)-Containing Group 6-8 (Cr, Mn, Fe, or Ru) Carbonyl Clusters: Synthesis, Reactivity, Electrochemistry, and Theoretical Calculations
| Autor: | Bo-Gaun Chen, 陳柏綱 |
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| Rok vydání: | 2008 |
| Druh dokumentu: | 學位論文 ; thesis |
| Popis: | 96 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. |
| Databáze: | Networked Digital Library of Theses & Dissertations |
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