臺灣博碩士論文加值系統

在過去的相關文獻中，多牙氮配位基2,7 –Di(2-pyridyl)-1,8-naphthyridine (bpnp)及其金屬錯合物已有一些報導，但對於鈀金屬的錯合物合成研究沒有報導。故在本篇論文中，利用Stille coupling，由2-(Tributylstannyl)pyridine及2,7-Dichloro-1,8-naphthyridine，在鈀金屬的催化之下，成功地合成出bpnp，並以其為主配位基，與零價的Pd2(dba)3及兩價的PdCl2(PhCN)2共同反應，合成出具有金屬金屬鍵的叁核鈀金屬錯合物[{Pd3Cl2(bpnp)2}Cl2]。由X光單晶繞射分析及電子密度分析儀器鑑定，顯示叁核鈀金屬的中心鈀，為一零價且六配位架構的型態存在。另外，在反應過程中，發現到bpnp會先個別地與Pd2(dba)3和PdCl2(PhCN)2反應，之後分別形成ㄧ錯合物，兩者再繼續互相反應，產生叁核鈀金屬錯合物。另ㄧ方面，將Pd3與CoCl2反應，藉由X光單晶繞射分析鑑定，得到陰離子為四氯化鈷的錯合物[Pd3Cl2(bpnp)2][CoCl4]。
叁鈀金屬錯合物[{Pd3Cl2(bpnp)2}Cl2]對於芳香族硼酸衍生物的水解，具有催化性質。相較於文獻報導以鈀金屬催化硼酸衍生物的探討，主要是以芳香族偶合的產物為主。但在我們的研究中，觀察到只有少量的偶合產物，主要以芳香酚或芳香還原產物。特別的是當使用4-甲氧基苯硼酸為試劑時，得到的是發生遷移的3-甲氧基苯酚。論文亦對於一系列的芳香族硼酸試劑，做一系統分析討論。

2,7 –Bis(2-pyridyl)-1,8-naphthyridine (bpnp) is a multiple pyridinyl nitrogen donor, which is capable of binding with metal ions in a chelating manner. In case of coordination with two metal ions, these centers are in close distance to have metal-metal interactions, which raises a subject of considerable interest. In our work, we tried to synthesize the dipalladium complex with bpnp. Indeed, we have successfully obtained a palladium complex chelated with bpnp, but in a trimetallic form. The structure of the complex is revealed by X-ray single crystal analysis.
For the first time, a mixed valence tripalladium species is constructed from the complexation of Pd(0), Pd(II) and bpnp. Detail structural formulation via X-ray diffraction analysis confirms the coordination mode. This tri-palladium complex was found to have catalytic activity on hydroxylation or reduction of phenylboronic acids

中文摘要 I
英文摘要 II
目錄 III
圖目錄 IV
表目錄 V
流程目錄 VI
第一章 緒論 1
第一節 多牙氮配位基2,7–di(2-pyridyl)-1,8-naphthyridine及其金屬錯合物 1
第二節 叁核鈀金屬錯合物之文獻回顧 4
第三節 鈀金屬錯合物催化之芳香族硼酸化合物自身偶合 7
第四節 研究目的 10
第二章 配位基及鈀金屬錯合物之合成與配位化學 11
第一節 配位基之合成 11
第二節 叁核鈀金屬錯合物之合成 12
第三節 叁核鈀金屬錯合物的反應性 14
第三章 叁核鈀金屬錯合物之催化反應探討 21
第四章 結論 30
第五章 實驗部分 31
實驗儀器 31
試劑來源及前處理 32
實驗操作 32
化合物的製備 32
參考文獻 45
附錄一 部分化合物之光譜圖 50
附錄二 部分錯合物之晶體資料 58

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