Synthesis and Reactivity of Ruthenium Vinylidene and Allenylidene Complexes

Date Issued
2005
Date
2005
Author(s)
Sung, Hui-Ling
DOI
en-US
URI
Abstract
在Cβ 含有環己烯取代基的釕金屬環丙烯基化合物，與矽烷基疊氮(TMSN3， (TMS = (CH3)3Si)) 反應可生成釕金屬疊氮化合物([Ru]-N3，([Ru] = Cp(PPh3)2Ru)) 及相關的有機產物。推測反應的機制是先由三甲基矽集團(TMS)與環丙烯基行親 電加成反應，隨即伴隨三甲基矽集團的水解而形成陽離子性的釕金屬亞乙烯基錯 合物([[Ru]=C=C(C6H9)CH2R][N3])。接著N3 攻擊Cα而第2 個三甲基矽集團加成 在環己烯取代基的雙鍵上，伴隨著一連串的電子轉移及脫氮氣(N2)而得到N 配位 在金屬上的釕金屬異氰化合物[[Ru]NCC(C6H10)CH2R][N3]，接著伴隨含有飽和六 環的有機物脫落及金屬疊氮化合物的生成。 將三苯基磷的配位基(PPh3)換成1,2-雙二苯基磷乙烷(dppe)，也可以合成出釕 金屬環丙烯基及呋喃化合物。而此呋喃化合物在室溫下容易與空氣中的氧氣作用 而形成O2 加成的釕金屬雙酯化合物。環丙烯基化合物則可與矽烷基疊氮作用而 形成穩定的N 配位釕金屬氰化合物。 若將環戊烯取代基(Cp)置換成茚取代基(indenyl ligand)，可以合成出含有茚 取代基的陽離子釕金屬亞乙烯基錯合物，此類化合物與鹼作用可行分子內的環化 反應而形成釕金屬環丙烯基或呋喃化合物。含有茚取代基的呋喃化合物在室溫下 可以穩定存在，而若與矽烷基疊氮作用則形成釕金屬疊氮化合物及相關的有機產 物。相較於含環戊烯取代基的釕金屬呋喃化合物與矽烷基疊氮作用的結果，是切 斷釕金屬與C 之間的單鍵而形成相關的有機呋喃產物；含茚取代基的釕金屬呋 喃化合物與矽烷基疊氮作用的結果是行開環的反應。 含茚取代基的陽離子性的釕金屬異氰化物(isocyanide complex)也可以被合 成出，此類的化合物在以二氯甲烷為反應溶劑中加入鹼去質子化可得釕金屬吖丙 啶基化合物(ruthenium azirinyl complex)；若反應溶劑改為丙酮則可得到含五員環 的釕金屬惡唑啉基化合物(ruthenium oxazolinyl complex)。 釕金屬亞丙二烯基化合物(ruthenium allenylidene complex)可以和格里納試劑 (Grignard reagent)在低溫下作用形成穩定的釕金屬-炔基(ruthenium σ−alkynyl complex)化合物。這一系列的化合物加入四氟硼酸(HBF4)質子化可以得到一系列 的釕金屬亞乙烯基化合物。反式- 氯基- 釕金屬- 炔基 (trans-chloride-ruthenium-alkyne) 化合物也可經由其相關的亞丙二烯基化合物和 格里納試劑作用而被合成出。加入四氟硼酸(HBF4)質子化後也可以得到一系列的 釕金屬亞乙烯基化合物。而此類的亞乙烯基化合物在溶液中容易脫去金屬而得到 相關的含有烯基和炔基(enyne)的有機化合物。 反式-異氰基-釕金屬-炔基(trans-isocyanide-ruthenium-alkyne)化合物，反式- 氯基-釕金屬-炔基(trans-chloride-ruthenium-alkyne)及反式-釕金屬二炔基(trans -ruthenium-dialkyne)化合物也可以順利的被合成出。此系列的化合物可以在空氣 中穩定存在。
Ruthenium cyclopropenyl complexes can be obtained by the deprotonation reaction of the ruthenium vinylidene complexes. When the vinylidene complexes containing an ester group at Cγ the reaction yielded thermodynamic ruthenium furyl complexes products. The reaction of the ruthenium cyclopropenyl complexes 6 containing a cyclohexenyl group at Cβ with TMSN3 (TMS = (CH3)3Si) yielded the ruthenium azide [Ru]-N3 ([Ru] = Cp(PPh3)2Ru) and free organic compound 7. The reaction may proceed by an electrophilic addition of a trimethylsilyl group to the three-membered-ring followed by hydrolysis to afford [[Ru]=C=C(C6H9)CH2R][N3]. Further nucleophilic addition of azide at Cα and electrophilic addition of a second trimethylsilyl group at the olefinic carbon of cyclohexenyl ring followed by loss of N2 gave the N-coordinated nitrile complexes [[Ru]NCC(C6H10)CH2R][N3] (9). Change the triphenylphosphine ligand for dppe ligand, the ruthenium furyl complex 12a and cyclopropenyl complex 12d containing cyclohexenyl group also can be obtained via deprotonation of vinylidene complexes 11. Further reaction of the metal furyl complex 12a with O2 yielded diester complex 13a. The reaction of cyclopropenyl complex 12d with TMSN3 gave the N-coordinated nitrile complex 14d as stable product. Change the cyclopentadienyl ligand for indenyl ligand, ruthenium vinylidenecomplexes 16 also can be obtained in high yield. Deprotonation of these vinylidene complexes yielded metal furyl complexes 18 when an ester substituent at Cγ and yielded cyclopropenyl complexes 17. The reaction of the ruthenium α-alkoxyfuryl complexes 18 containing indenyl group with TMSN3 gives the ruthenium azide [Ru]-N3 ([Ru]=(η5-C9H7)(PPh3)2Ru) and organic compounds 5. Treatment of the cyclopropenyl complexes 17 with TMSN3 also affords the ruthenium azide and organic compounds via opening the three-membered ring. Ruthenium isocyanide complex 21 containing indenyl ligand can be obtained in high yield. By deprotonation of these isocyanide complex yield ruthenium azirine 22 in CH2Cl2 and yield oxazoline complexes 23 in acetone, respectively. The cationic ruthenium allenylidene complex 24 containing a dppe ligand can be synthesized by the literature method. Then the allenylidene complex reacts with Grignard reagents to yield the σ−alkynyl derivatives 25a−25d. Protonation of 25a with HBF4·Et2O leads to the vinylidene complex 27a as the final product. Similarly, the vinylidene complex 26 also can be obtained. Protonation of complex 25b yielded the unexpected product 28b. The trans-chloride-ruthenium-allenylidene complexes react with Grignard reagents to yield the σ−alkynyl derivatives 29. Protonation of 29 with HBF4·Et2O also leads to the vinylidene complex 30. Complex 30 is stable in solid state. When dissolved inCH2Cl2 at room temperature the organic enyne product 31 can be obtained through the demetalation reaction. The trans-isocyanide-ruthenium-alkyne complexes 33 also can be obtained in high yield. The trans-chloride-ruthenium-alkyne 34 and dialkynyl complex 36 containing cyclohexenyl group also can be obtained in moderate yield. Both complexes are stable.
Subjects
釕金屬亞乙烯基
釕金屬亞丙二烯基
環丙烯
vinylidene
allenylidene
cyclopropene
Type
thesis
File(s)
Loading...
Thumbnail Image
Name

ntu-94-D90223024-1.pdf

Size

23.31 KB

Format

Adobe PDF

Checksum

(MD5):7d2741b922f8fe9f209b062a465b6b39

臺大位居世界頂尖大學之列，為永久珍藏及向國際展現本校豐碩的研究成果及學術能量，圖書館整合機構典藏（NTUR）與學術庫（AH）不同功能平台，成為臺大學術典藏NTU scholars。期能整合研究能量、促進交流合作、保存學術產出、推廣研究成果。

To permanently archive and promote researcher profiles and scholarly works, Library integrates the services of “NTU Repository” with “Academic Hub” to form NTU Scholars.

總館學科館員 (Main Library)
醫學圖書館學科館員 (Medical Library)
社會科學院辜振甫紀念圖書館學科館員 (Social Sciences Library)

開放取用是從使用者角度提升資訊取用性的社會運動，應用在學術研究上是透過將研究著作公開供使用者自由取閱，以促進學術傳播及因應期刊訂購費用逐年攀升。同時可加速研究發展、提升研究影響力，NTU Scholars即為本校的開放取用典藏（OA Archive）平台。（點選深入了解OA）

  • 請確認所上傳的全文是原創的內容，若該文件包含部分內容的版權非匯入者所有，或由第三方贊助與合作完成，請確認該版權所有者及第三方同意提供此授權。
    Please represent that the submission is your original work, and that you have the right to grant the rights to upload.
  • 若欲上傳已出版的全文電子檔，可使用Open policy finder網站查詢，以確認出版單位之版權政策。
    Please use Open policy finder to find a summary of permissions that are normally given as part of each publisher's copyright transfer agreement.

Built with DSpace-CRIS software - Extension maintained and optimized by 4Science