含8-羥基喹啉之錸金屬有機錯化合物的合成與性質探討

Synthesis, Characterization and Properties of 8-Hydroxyquinoline-Containing Rhenium Complexes

李育凭(Yu-Ping Lee)

指導教授 ： 曾添文

國立臺北科技大學/工程學院/化學工程研究所/碩士(2009年)

https://doi.org/10.6841/NTUT.2009.00138

摘要

在本研究中，我們利用8-羥基喹啉及十羰基二錸以甲苯作為溶劑，在水熱反應中合成了化合物1—9，所得化合物分為兩部份討論，其中化合物1—4為第一部份，主題為8-羥基喹啉及喹喔啉衍生物，於錸金屬化合物中交聯偶合反應之研究。我們利用8-羥基喹啉及喹喔啉衍生物與十羰基二錸進行水熱反應，經由此水熱反應我們成功的合成了四個錸金屬有機化合物，在此反應中8-羥基喹啉及喹喔啉衍生物經由碳-碳交聯偶合反應結合成新的有機配子。本類型使用未活化之有機分子進行碳-碳交聯偶合反應的報導非常少見，且就我們所知這是第一個有關於以兩個不同且未經活化的有機雜環分子，可藉著錸金屬錯化合物進行碳-碳交聯偶合反應。而第二部份探討化合物5—9，主題為含8-羥基喹啉之單核及雙核錸金屬有機錯化合物之合成及性質探討。在此研究中，我們利用8-羥基喹啉設計且合成兩個雙核的錸金屬有機錯化合物5和化合物6，及三個單核的錸金屬有機錯化合物7—9。並針對這些錸金屬有機錯化合物的電化學及光物理性質做了初步的探討。在研究中發現，化合物[{(CO)3Re}2(C9H7NO)2(C10H8N2)] (5)具有高度的電化學穩定性，其分配常數(comproportionation constant, KC)為1.98 × 105。另外，發現單核的錸金屬有機錯化合物(7—9)，於波長500 nm處之發光強度，會受到溶液中的鹽酸濃度影響。若鹽酸濃度介於10-2 M到10-3 M之間時，單核的錸金屬有機錯化合物的發光強度會隨著鹽酸濃度增加而增強。

關鍵字

錸金屬化學 ； 8-羥基喹啉喹喔啉衍生物 ； 碳-碳交聯偶合反應 ； 化學感測器

並列摘要

Nine rhenium organometallic complexes were synthesized under solvothermal reaction conditions. These complexes were dlassified into two parts for studing. In part I focus on the cross-coupling of unactivated arenes with rhenium complexes. In this part four dirhenium organometallic complexes [(CO)3Re(L)]2 (1—4) were synthesized by using 8-hydroxyqunoline and quinoxaline derivatives under solvothermal reaction condition. Among then there were two ligands exhibited the unprecedented cross-coupling reaction of unactived arenes. To our best knowledge, this is the first report of rhenium joined dehydrogenative cross-coupling between two different ligands with unactivated arenes. And in part II of this thesis is to study the 8-hydroxyquinoline containing mono and binuclear rhenium complexes. Five rhenium organomatellic complexes were successful synthesized under hydrothermal reactions and characterized. These complexes could be simply classified as monorhenium complexes and dirhenium-containing complexes. Their electrochemical and photophysical properties have been examined. In our preliminary research, the calculated comproportionation constant shown the stability of complex [{(CO)3Re}2(C9H7NO)2(C10H8N2)] (5) (KC = 1.98 × 105) in electrochemistry. From photophysical examining showed that the luminosity of three mononuclear complexes (7—9) at 500 nm will change with the variate of concentration of HCl in solutions.

並列關鍵字

Rhenium ； 8-Hydroquinoline ； Quinoxaline ； Cross-Coupling ； Structure ； Sensor

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