具Non-innocent配基之鍺烯與錫烯

Non-innocent Ligand Supported Germylenes and Stannylenes

陳崑豪(Kun-Hao Chen)

指導教授 ： 邱靜雯

國立臺灣大學/理學院/化學研究所/碩士(2021年)

https://doi.org/10.6342/NTU202101278

摘要

為了研究二價金屬烯的反應性，我們成功地合成了具non-innocent配基之鍺烯與錫烯化合物。具non-innocent配基之鍺化合物可以當作是吡啶環化的N-雜環鍺烯（2）或中性的α-亞氨基吡啶配位的鍺零價化合物（2'）。在2與鹽酸和三氯化硼的反應中觀察到鍺中心與配位基的協同作用，證實在二價鍺原子上存在一個空的p軌域。接著我們發現配位基容易從2轉移到二氯化鍺或二氯化錫之中，並且伴隨著金屬元素鍺沉澱出來，反映了中心零價鍺原子的高電子密度特性。另外也使用兩個當量的四氯-鄰-苯醌進行四個電子的氧化反應，進一步驗證了2具有零價鍺的性質，同時得到了六配位的四價鍺化合物。此外，我們還利用二[二(三甲基甲矽基)氨基] 錫與α-亞氨基吡啶配位基進行轉氨基作用，製備了吡啶配位的二氨基錫烯。接著合成與鑑定含錫基和吡啶基雙牙配位基的釕金屬錯合物，並將其用於酮的氫轉移催化之中。

關鍵字

鍺烯 ； 錫烯 ； non-innocent配基 ； 錫基釕金屬錯合物 ； 氫轉移催化

並列摘要

To explore the reactivity of divalent metallylene, the non-innocent ligand supported germylene and stannylene were successfully synthesized. The non-innocent ligand supported germanium compound can be viewed as a pyridine annulated N-heterocyclic germylene (2) or a neutral α-iminopyridine coordinated germylone (2’). The Ge-ligand cooperation was observed in the reaction of 2 with HCl and BCl3, confirming the presence of a vacant p orbital at the Ge(II) atom. The readily transferring of the ligand from 2 to ECl2 (E = Ge, Sn) with the extrusion of metallic germanium reflects the electron richness of the central Ge(0) atom. The germylone character of 2 was further verified via four-electron oxidation with two equivalents of tetra-chloro-o-benzoquinone to give a six-coordinated germanium (Ⅳ) adduct. Besides, pyridine-coordinated diamido stannylene prepared from transamination of corresponding α-aminopyridine with Sn[N(TMS)2]2 was utilized as a bidentate ligand in Ru(Ⅱ) cymene complex, a stannyl-Ru complex that is fully characterized and applied in catalytic transfer hydrogenation reaction of ketones.

並列關鍵字

germylene ； germylone ； non-innocent ligand ； stannylene ； transfer hydrogenation

參考文獻

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