臺灣博碩士論文加值系統

具有氧化還原活性取代基二茂鐵的釕金屬亞丙乙烯基錯合物可經由釕金屬之三苯基膦或一,二-雙苯基膦乙烷、氯及環戊二烯配位之化合物在甲醇中和含有末端碳-碳不飽和三鍵之鐵金屬乙炔醇類化合物反應而成。釕金屬亞丙乙烯基化合物與格林納試劑進行選擇性的親核加成反應在亞丙乙烯基的γ碳上，可得到中性釕金屬之乙炔基之錯合物。γ碳上含有丙烯基之乙炔基錯合物進行氫化反應而得到陽離子釕金屬亞乙烯基錯合物。此化合物行獨特之分子內[2+2]環化反應，再經由開環形成不同的亞乙烯基化合物。 將釕金屬之環戊二烯、一,二-雙苯基膦乙烷及氯配位之化合物在等量之含有末端碳-碳不飽和三鍵的亞乙烯基錯合物，以及過量的六氟磷化銨在含有甲醇的二氯甲烷溶液中反應，製備出雙核釕金屬之亞乙烯基化合物。此化合物在如甲醇鈉存在的鹼性環境中進行去質子化反應，形成具有亞乙烯基和乙炔基橋接的雙核釕金屬錯合物。此化合物針對不同官能基之一級鹵烷類在二氯甲烷中反應得一系列之二價陽離子之釕金屬亞乙烯基錯合物。同樣對具有氰基之亞乙烯基錯合物在鹼性環境中進行去質子化反應，經由核磁共振光譜鑑定，可得具有環丙烯三員環和亞乙烯為配位基的雙核釕金屬錯合物。而具有乙炔基之亞乙烯基錯合物在鹼性環境中則無質子化反應。 具有異氰基、環庚烯與1,2-雙苯基膦乙烷之鉬金屬錯合物在重氫四氫(口夫)喃溶液中進去質子化反應，由低溫核磁共振光譜鑑定，會經由雜環三圓環之不飽和氮丙啶中間物，再經由羰基嵌入雜環得到不甚穩定之噁唑類錯合物。在丙酮溶液中直接和甲醇鈉行去質子化反應也可得到相同之錯合物。噁唑類錯合物在含有碘甲烷之甲苯溶液中反應。此反應產生之離子錯合物，以核磁共振光譜和X射線單晶繞射鑑定之，確定為含異氰基之陽離子鉬金屬錯合物。

Ferrocenyl ferrocenyl-substituted allenylidene complexes [(η5-C5H5)(L)2Ru=C=C=C (Ph)(Fc)][PF6] (L = PPh3, 1a; 1/2 dppe, 1b) was prepared by treatment of a methanol solution of (η5-C5H5)(L)2RuCl (L = PPh3, 1/2 dppe) with the propargylic alcohol 1-ferrocenyl-1-phenylprop-2-yn-1-ol in the presence of NH4PF6. Reaction of 1a-b with Grignard reagent RMgBr or MeLi in THF yielded the neutral acetylide complexes 2a-3d (η5-C5H5)(L)2Ru-C≡CCPh(Fc)R (Fc = (η5-C5H4)Fe(η5-C5H5), L = PPh3, R = CH2CH=CH2, 2a; R = CH2C≡CH, 2b; R = CH2C(CH3)=CH2, 2c; L = 1/2 dppe, R = CH2CH=CH2, 3a; R = CH2C≡CH, 3b; R = CH2C(CH3)=CH2, 3c; R = Me, 3d). Complexes 2a-3d undergo protonation reactions affording the corresponding vinylidene complexes 4a-5d [(η5-C5H5)(L)2Ru=C=CHCPh(Fc)R]+ (L = PPh3 ,R = CH2CH=CH2, 4a; R = CH2C≡CH, 4b; R = CH2C(CH3)=CH2, 4c; L = 1/2 dppe, R = CH2CH=CH2, 4a; R = CH2C≡CH, 4b; R = CH2C(CH3)=CH2, 4c; R = Me, 4d). The cationic complex 4a in methanol solution for 12h followed by subsequent addition of NaOMe to give the new neutral acetylide complex (η5-C5H5)(PPh3)2Ru-C≡C-CH2C (Ph)([Fc])CH=CH2 (6). This transformation was proposed that a metathesis process of the terminal vinyl group with the C=C of the vinylidene group as mechanism. The presence of a gem-ferrocenylphenylmethylene moiety at the vinylidene ligand with the appropriate terminal vinyl or alkynyl group along with the correct steric environment implements such a specific reactivity in the ruthenium vinylidene complexes. The bisvinylidene complex [Ru]=C=C(Ph)CH2CH=C=[Ru]2+ (8) ([Ru] = (η5-C5H5) (dppe)Ru) can be obtained from the reaction of {[Ru]=C=CPhCH2C≡CH}+ with [Ru]Cl in the presence of NH4PF6 and methanol. Deprotonation of the bisvinylidene complex 8 formed the alkylnyl vinylidene complex [Ru]=C=C(Ph)CH2C≡C-[Ru]+ (9), which was alkylated by primary alkyl halide to give the ruthenium bisvinylidene complex [Ru]=C=C(Ph)CH2C(CH2R)=C=[Ru]2+ (R = CN, 10a; R = COOMe, 10b; R = C≡CH, 10c). Deprotonation of 10a by NaOMe is followed by a cyclization process yielding the stable complex 11, containing a three-membered carbocyclic ring ligand, which is characterized by NMR spectroscopy. No deprotonation reactions of 10c was observed under various basic conditions. Deprotonation reaction of the cationic isocyanide complexes of molybdenum {[Mo]-C≡NCH2C6F5}Br ([Mo] = (η7-C7H7)(dppe)Mo), with NaOMe in the presence of acetone leads to the synthesis of oxazolinyl complexes 13. This reaction proceeds via an azirinyl intermediate detected by NMR spectra followed by insertion of a carbonyl group into the C-C single bond of the three-membered ring. Regiochemistry of the C-C bond formation is different from that in the photolytically induced insertion of carbonyl compound to organic azirine. Methyl substituted isocyanide complex 14 containing a stereogenic carbon center was obtained by treatment of iodomethane with oxazolinyl complex 13. Complex 14 are determined by X-ray diffraction studies.

Contents
Structure and Numbering of Complexes vii
Reaction Scheme ix
中文摘要 xii
Abstract xiii
Introduction 1
A-1 Metal Vinylidene Complexes 1
A-2 Reactivity of Enyne in the Presence of Transition Metals 5
A-3 Dimetallic Vinylidene Complexes 9
Results and Discussions 15
Chapter 1 Reactions of Ruthenium Vinylidene Complexes with A Ferrocenyl Substituents 15
1-1 Synthesis of Allenylidene Complexes with A Redox-active Moiety at Cγ 19
1-2 Synthesis of Acetylide Complexes with A Stereogenic Center at Cγ 24
1-3 Synthesis Reactivity of The Ruthenium Vinylidene Complexes 28
Chapter 2 Dinuclear Ruthenium Vinylidene Complexes and Their Deprotonation Reactions 45
2-1 Bisvinylidene complex 45
2-2 Deprotonation of The Bisvinylidene Complex 50
2-3 Preparation of Other Dinuclear Ruthenium Vinylidene Complexes 52
2-4 Deprotonation Reactions of Dinuclear Ruthenium Vinyliene Complex 55
Chapter 3 η7-cycloheptatrienyl-molybdenum azirinyl, oxazolinyl, and isocyanide complexes 60
3-1 Molybdenum azirinyl complexes 61
3-2 Molybdenum oxazolinyl complexes 64
3-3 Alkylation of oxazolinyl complex 67
Concluding Remark 73
Experiment section 75
B-1 Experimental Procedures in Chapter 1 75
B-2 Experimental Procedures in Chapter 2 92
B-3 Experimental Procedures in Chapter 3 99
References 103
Supporting Information 113

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