臺灣博碩士論文加值系統

中文摘要
將釕金屬乙炔基化合物與一系列的親電子試劑作用，可生成釕金屬亞乙烯基化合物 [Cp(PPh3)2Ru=C=C(C6H9)CH2R][X] (R=CO2CH3, 3a; CO2C2H5, 3b; C6H5, 3c; C10H7, 3d; C6H4CF3, 3e; C6H4CN, 3f; CH=CHCO2CH3, 3g; C6F5, 3h)。 此釕金屬亞乙烯基化合物在丙酮溶液中可藉由脫去Cg上的一個氫，而形成釕金屬環丙烯基（cyclopropenyl）化合物[Cp(PPh3)2Ru-C=C(C6H9)CHR] (R=C6H5, 4c; C10H7, 4d; C6H4CF3, 4e; C6H4CN, 4f)。
取含酯基的亞乙烯基化合物，在室溫下與反應，可得到釕金屬■喃化合物[Cp(PPh3)Ru-C=C(C6H9)CHC(OR)O] (R=CH3, 5a; C2H5, 5b)。釕金屬亞乙烯基化合物C■上不同的取代基決定不同的反應結果。另外，當亞乙烯基化合物有五氟苯取代基時，除了形成脫氫的環丙烯基化合物外，還可以形成甲氧基取代一個氟的環丙烯基化合物。
在含氧的環境下，釕金屬■喃化合物會與氧氣作用，生成 endoperoxide 的中間物，再形成含酯基釕化合物[Cp(PPh3)Ru-O-C(O)=C(C6H9)CHC(OR)O](R=CH3, 6a; C2H5, 6b)。此類的酯基釕化合物再與碘甲烷或質子酸反應而成有機酯類化合物。
釕金屬環丙烯基化合物在四氫■喃溶劑中，可與疊氮三甲基矽烷（azidotrimethylsilane）反應，而形成釕氰基化合物 [Cp(PPh3)Ru]-CN 及有機的三■(triazole)化合物。其反應過程是先形成亞乙烯基化合物，然後疊氮陰離子攻擊C■，再經由一連串的電子轉移及水解反應而形成最終產物。
若以■喃化合物與疊氮三甲基烷試劑反應則產生不同的反應結果；金屬的部分已變為疊氮化合物，而■喃基部分則脫落變為有機■喃化合物。

ABSTRACT
Reaction of complex Cp(pph3)2RuCl (1) with C6H9CCH gave a ruthenium acetylide complex (2). Treatment of complex 2 with alkyl halide afforded ruthenium vinylidene complexes [Cp(PPh3)2Ru=C=C(C6H9)CH2R][X] (R=CO2CH3, 3a; CO2C2H5, 3b; C6H5, 3c; C10H7, 3d; C6H4CF3, 3e; C6H4CN, 3f; CH=CHCO2CH3, 3g; C6F5, 3h). Further reaction of 3a and 3b with n-Bu4NOH at room temperature afforded [Cp(PPh3)Ru-C=C(C6H9)CHC(OR)O] (R=CH3, 5a; C2H5, 5b).
The same reaction carried out at low temperature, yielded cyclopropenyl complexes [Cp(PPh3)2Ru-C=C(C6H9)CHCO2R] (R=CH3, 4a; C2H5, 4b) as the major product and furan complexes 5 as the minor product. Treatment of complexes 3c-3f with n-Bu4NOH afforded cyclopropenyl complexes [Cp(PPh3)2Ru-C=C(C6H9)CHR]
(R=C6H5, 4c; C10H7, 4d; C6H4CF3, 4e; C6H4CN, 4f ). Interestingly, however, deprotonation of complex 3h with n-Bu4NOH yielded the cyclopronenyl complex 4h and 14 in which one of fluorine atom was substituted by an OMe group. The pure 14 was obtained if the reaction time is longer than 3 days. Ruthenium cyclopropenyl complex 4i was obtained from the reaction of [Cp(PPh3)2Ru-C=C(Ph)CH2CH=CHCO2CH3]+ with n-Bu4NOH at the intial stage. The reaction of complex [Cp(PPh3)2Ru-C=C(Ph)CHCH=CHCO2CH3](4i) with (CH3)3SiN3 yields [Cp(PPh3)2Ru]-CN (12) and an organic product Ph-C=C(CH2CO2CH3)N2NH (13) which contains a five-membered triazolate ring by cleavage of the C=C double bond of the cyclopropenyl ring.
The ruthenium furan complex 5 reacted with (CH3)3SiN3 to afforded [Cp(PPh3)2Ru]-N3 and organic furan compound HC=C(Ph)CH=C(OR)O (R=CH3, 8m; C2H5, 8n). Exposure of the furan complexes 5 in air for several days yielded ester complexes [Cp(PPh3)Ru-O-C(O)=C(C6H9)CHC(OR)O] (R=CH3, 6a; C2H5, 6b) via endoperoxide intermediate by Diels-Alder reaction.
Treatment of the ester complexes 6 with protic acids such as CH3COOH and CF3COOH afforded [Ru]-O2CR (R=CH3, CF3) and organic compound HO2CC(C6H9)=CHCO2R. (R=CH3, 10m; C2H5, 10n). Treatment 6 with CH3I afforded ruthenium halide [Ru]-I and diester compound CH3O2CC(C6H9)=CHCO2R. (R=CH3, 11m; C2H5, 11n).

Contents
Structure and Numbering of Compounds III
Reaction Scheme 1-6 VI
Abstract XII
Chapter 1 Background 2
Chapter 2 Synthesis of Vinylidene Complexes
2-1 Introduction 5
2-2 Results and Discussion 12
Chapter 3 Synthesis of Cyclopropenyl Complexes
3-1 Introduction 17
3-2 Neutral cyclopropenyl complexes 20
3-3 The reactivity of cyclopropenyl complexes containing a pentafluorophenyl substituent 30
Chapter 4 Reaction of Cyclopropenyl Complexes with TMSN3
4-1 Introduction 43
4-2 Results and Discussion 45
Chapter 5 Synthesis and Reaction of Furan Complexes
5-1 Synthesis of furan complexes 58
5-2 Reactions of furan complexes with TMSN3 64
Chapter 6 Conclusion 68
Chapter 7 Experimental Section 70
References 109

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