含吡咯醛之釕金屬丙二烯錯合物的合成與反應研究

Reactions of Ruthenium Vinylidene Complexes with Terminal Alkyne Containing Pyrrole Carbaldeyhde

賈丕業(Pi-Yeh Chia)

指導教授 ： 林英智

國立臺灣大學/理學院/化學研究所/碩士(2011年)

https://doi.org/10.6342/NTU.2011.03124

摘要

利用釕金屬錯合物[RuCp(PPh3)2Cl]，與N-炔丙基吡咯有機化合物1反應，形成釕金屬亞乙烯基錯合物2，將錯合物2溶於二氯甲烷中，與溶在甲醇中的氨進行反應，可得到釕金屬費雪型胺基碳烯錯合物5；然而利用一級氨在相同的反應環境下與錯合物2反應，則可得到環化後的釕金屬碳烯錯合物8。利用鹼與錯合物2反應可得到去質子化後的中性的釕金屬乙炔基錯化合物3，錯合物3與烷化試劑反應可得雙取代的亞乙烯基錯合物4a-b，之後利用鹼再進行分子內的環化反應可得到釕金屬含雜環呋喃的錯化合物6a-b，其中6a錯化合物則會伴隨著[1,3]苄基轉移，而得到釕金屬錯合物7a。利用釕金屬錯合物[RuCp(PPh3)2Cl]與含吡咯苯甲基乙炔有機化合物9在二氯甲烷中反應，可得到釕金屬亞乙烯基錯化合物10，當溶劑改變為甲醇時，則會得到具七環雙取代的釕金屬亞乙烯基錯化合物11，而其環化過程中可能會先形成錯合物10。亞胺烯炔有機物12與釕金屬錯合物[RuCp(PPh3)2Cl]在二氯甲烷中反應，則可得到具六環帶正電亞胺離子的釕金屬錯合物。

關鍵字

釕金屬 ； 烯炔 ； 吡咯醛

並列摘要

Treatment of the N-propargyl pyrrole 1 with [Ru]-Cl ([Ru] = Cp(PPh3)2Ru) in the presence of KPF6 in CH2Cl2 afforded the vinylidene complex 2. A solution of 2 in CH2Cl2 was reacted with an aliquot of NH3 solution in methanol at room temperature to yield the Fischer-type aminocarbene ruthenium(II) complex 5. The reaction of complex 2 with primary amine in CH2Cl2, however, yielded the ruthenium(II) carbene complex 8. Deprotonation of 2 with base afforded a neutral acetylide complex 3. The reaction of complex 3 with haloacetates in the presence of KPF6 then afforded the disubstituted vinylidene complexes 4a and 4b. In the deprotonation reactions of these disubstituted vinylidene complexes containing ester groups, the furyl complexes 6a and 6b were obtained, respectively. For the furyl complex 6a containing an O-benzyl group, a subsequent 1,3-migration of the benzyl group is observed to yield the lactone product 7a. The reaction of [Ru]-Cl with compound 9 and NH4PF6 in CH2Cl2 for 1 day yielded the vinylidene complex 10. When the solvent of the reaction was changed from CH2Cl2 to methanol, the reaction gave the cyclization product 11, possibly via the intermediate complex 10. Reaction of iminenyne 12 with [Ru]-Cl and NH4PF6 in CH2Cl2 for 1 day yielded the ruthenium complex 13 containing cationic imine group. Complexes 3, 4a and 13 are fully characterized by X-ray diffraction analysis.

並列關鍵字

ruthenium ； enyne ； pyrrolecarbaldehyde.

參考文獻

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