| Summary: | 碩士 === 國立臺灣師範大學 === 化學系 === 102 === 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.
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