臺灣博碩士論文加值系統

摘要
在低自旋鐵族錯合物中， 鋨氨(II，III)為探討最少的錯合物，主要原因乃因Os(NH3)52+金屬中心還原力太強，難以掌握適當的實驗條件， trans-[Os(en)2(h2-H2)]2+ 錯合物因有Os(II)®H2的backbonding (MLCT)回饋鍵結，而使Os(II) 錯合物較為穩定，因此可用以取代Os(II) ammine錯合物，探討所形成錯合物的性質。 不但如此，由於具有水溶性，因此適用於生物系統的探討。trans-[Os(en)2(h2-H2)L]2+ 錯合物中的h2-H2在NMR中有一獨特的訊號範圍(-8.47~-13.90 ppm)，並隨不同的配位基化學位移亦隨之改變。
本文乃從電子吸收光譜，1H-NMR及形成反應動力學角度探討trans-[Os(en)2(h2-H2)L]2+ (L=ImH, py, Cl-, H2PO4-, GMP及AMP) 錯合物的性質，比較GMP及AMP錯合物與其他單鍵結位置錯合物所得結果，傾向於Os(II)金屬中心經由GMP的N-7鍵結，而AMP則是經由N-1鍵結。

Trans-[Os(en)2(h2-H2)L]2+ metal canter has replaced Os(NH3)52+ for the investigation of Os(II) ammine complexes due to the strong reducing power of Os(NH3)52+ moiety which limits the study of Os(NH3)5L2+ complexes to the organic solvents. Trans-[Os(en)2(h2-H2)L]2+ complexes were stabilized by the Os(II) to H2 backbonding to such an extent that we were able to investigate the Os(II) complexes in the aqueous solution. Trans-[Os(en)2(h2-H2)L]2+ complexes were characterized by a unique signal of the 1H-NMR spectra in the 0~-14 ppm region, and its chemical shift was sensitive to the ligand used.
In this work we studied the spectroscopic (electronic and 1H-NMR) properties and the kinetics of formation of both AMP and GMP complexes of trans-[Os(en)2(h2-H2)L]2+. In order to understand the preferred coordination site of the metal center, properties of complexes with L= imH, py, Cl-, H2PO4-, HPO42- were also investigated.

總目錄
中文摘要 I
英文摘要 II
總目錄 III
圖目錄 V
表目錄 VIII
第一章緒論 1
第二章實驗 9
一.藥品及材料 9
二.合成 11
三.蒸餾水系統 15
四.去氧處理 15
五.溶液配製 17
六.分析儀器及校正方法 18
第三章結果 23
一.紫外-可見光吸收光譜 23
二. 磁核共振光譜 29
三. trans-[(en)2Os(η2-H2)L]2+錯合物的形成反應動力學 39
第四章討論 49
一.紫外-可見光吸收光譜 49
二. 磁核共振光譜 51
三. trans-[(en)2Os(η2-H2)L]2+錯合物的形成反應動力學 58
第五章結論 62
參考書目 63
附錄一 Sydnone Complexes of Pentacyanoferrate(II) A1
附錄二 The Oxidative Dehydrogenation on the α-carbon of 4-Pyridylacetonitrile Complexes of Pentaammineruthenium(II)
A2

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