謝明惠M, Shieh簡思環2019-09-042014-8-252019-09-042014http://etds.lib.ntnu.edu.tw/cgi-bin/gs32/gsweb.cgi?o=dstdcdr&s=id=%22GN060142059S%22.&%22.id.&http://rportal.lib.ntnu.edu.tw:80/handle/20.500.12235/1004461. Te/M/CO (M = Cr、Mo 及 W) 系統之研究 以不同莫耳比例之 TeO2、Cr(CO)6 和 Et4NBr 於 1.5 M 鹼性 MeOH 溶液中加熱迴流 (superheating)，可分別得化合物 [Te2Cr4(CO)18]2─ (1) 和 [Te7Cr6(CO)20]4─ (2)。反之，若此一鍋化合成於 1 M 鹼性 MeOH/MeCN 混合溶液及 45 oC 下反應，則形成化合物 [Te7Cr4(CO)14]4─ (3)。當改變主族來源，進一步混合 Te powder、M(CO)6 (M = Mo 和 W) 及Et4NBr 於 1 M 或 2 M 鹼性 MeOH/MeCN 混合溶液及 45 oC 下反應，亦獲得一系列新穎 金屬團簇物 [Te7Mo6(CO)20]4─ (4)、[Te6Mo6(CO)15]4─ (5)、[Te4W4(CO)14]4─ (6) 及 [Te6W5(CO)12]4─ (7)。此外，化合物 1 和 6 可藉由加入 TeO2/KOH 或置於加熱環境下，可分別擴核形成化合物 2 和 7。而化合物 4 與 Mo(CO)6/KOH 反應，則降解形成化合物 5。有趣的是，當化合物 7 與 I2 反應，可生成等電子結構 [Te6W5(CO)12]2─ (8)。其化合物之生成、結構轉換及相關性質亦藉由理論計算進一步驗證。 2. Se/Fe/CO/Cu/NHC 系統之研究 以一鍋化方式混合加入團簇物 [SeFe3(CO)9Cu2(MeCN)2] (1)、KOBut 和一系列咪唑啉鹽類 (1,3-dimethylimidazolium iodide (Me2Im•HI)、1,3-dimethylbenzimidazolium iodide (Me2BenzIm•HI)、1,3-diisopropylbenzimidazolium iodide (iPr2BenzIm•HI) 和 4,5-dichloro-1,3-dimethylimdazolium iodide (4,5-Cl2Me2Im•HI) 反應，分別得到化合物 [SeFe3(CO)9Cu2(Me2Im)2] (2)、[SeFe3(CO)9Cu2(Me2BenzIm)2] (3)、[SeFe3(CO)9Cu2(iPr2BenzIm)2] (4) 及 [SeFe3(CO)9Cu2(4,5-Cl2Me2Im)2] (5)。此外，於氧氣環境下化合物 1─5 可進行芳香環硼酸之耦合反應。其化合物之生成、催化反應及相關性質亦藉由理論計算進一步驗證。Abstract 1. Te/M/CO (M = Cr, Mo, W) System The reactions of appropriate ratios of TeO2, Cr(CO)6, and Et4NBr in superheated 1.5 M KOH/MeOH solutions led to the formation of clusters [Te2Cr4(CO)18]4─ (1) and [Te7Cr6(CO)20]4─ (2). Otherwise, a similar one-pot reaction in 1 M KOH/MeOH/MeCN solutions at 45 oC led to the formaton of cluster [Te7Cr4(CO)14]4─ (3). When the chalcogen’s source was changed to Te powder, a series of novel cluster anions [Te7Mo6(CO)20]4─ (4), [Te6Mo6(CO)15]4─ (5), [Te4W4(CO)14]4─ (6), and [Te6W5(CO)12]4─ (7) were obtained directly from the reactions of Te powder with M(CO)6/Et4NBr (M = Mo and W) in 1M or 2 M KOH/MeOH/MeCN solutions at 45 oC. When clusters 1 and 6 were treated with TeO2/KOH or in the heating conditions, the larger clusters 2 and 7 were produced. Cluster 4 could also be reconverted to cluster 5 by the addition of Mo(CO)6/KOH/MeOH/MeCN solutions. More interesting, when cluster 7 was reacted with I2, the isoelectronic cluster [Te6W5(CO)12]2─ (8) was formed. Furthermore, the nature, structural transformation, and electrochemical property of these resultant clusters are discussed and elucidated by DFT calculations. 2. Se/Fe/CO/Cu/NHC System The one-pot reaction of cluster [SeFe(CO)9Cu2(MeCN)2] (1) with KOBut/imidazolium salts (1,3-dimethylimidazolium iodide (Me2Im•HI), 1,3-dimethylbenzimidazolium iodide (Me2BenzIm•HI), 1,3-diisopropylbenzimidazolium iodide (iPr2BenzIm•HI), and 4,5-dichloro-1,3-dimethylimidazolium iodide), a series of novel clusters [SeFe3(CO)9Cu2(Me2Im)2] (2), [SeFe3(CO)9Cu2(Me2BenzIm)2] (3), [SeFe3(CO)9Cu2(iPr2BenzIm)2] (4), [SeFe3(CO)9Cu2(4,5-dichloro-1,3-dimethylimidazolin-2-ylidene)2] (5) were formed, respectively. In addition, clusters 1─5 were able to mediate the dimerization of arylboronic acid under oxygen atmosphere. Furthermore, the nature, the catalysis, and electrochemical property of these resultant clusters are diacussed and elucidated by DFT calculations.鉻钼鎢碲硒鐵CrMoWTeSeFe