Organometallic Alkynyl Complexes Synthesis and Reactivity

• Main Authors: Guo-Hao Chen, 陳國豪
• Other Authors: Tsung-Mei Chin
• Format: Others
• Language: zh-TW
• Published: 2007
• Online Access: http://ndltd.ncl.edu.tw/handle/94048875223565809722

碩士 === 中國文化大學 === 應用化學研究所 === 95 === Abstract Reaction of the compound 1f with an equimolar amount of CpL2RuCl (2) (2a, L = PPh3; 2b, L = PEt3; 2c, L2= dppe; 2d, L2 = dppp) in the presence of AgPF6 in CH2Cl2 at room temperature affords cationic vinylidene complexes {CpL2Ru=C=CHCH2C(Ph)2CH=CH2}[PF6] (3) (3a, L = PPh3; 3b, L2 = PEt3; 3c, L2= dppe). Deprotonation of complexes 3 by NaOMe yields neutral acetylide complexes CpL2RuC≡CCH2C(Ph)2C≡CH (4a, L = PPh3; 4b, L = PEt3; 4c, L2 = dppe) isolated as yellow powder in high yield. Alkylation of complexes 4a, and 4b with various primary alkyl halides afford corresponding cationic ruthenium vinylidene complexes CpL2Ru=C=CH2(R2)CH2C(Ph)2CH=CH2 (5a, L = PEt3, R2 = C≡CH; 5b, L = PEt3, R2 = CH=CH2; 5c, L = PEt3, R2 = COOMe; 5d, L = PEt3, R2 = COOEt; 5f, L = PEt3, R2 = Ph; 5g, L = PPh3, R2 =CH3). Thermolysis of cationic vinylidene complexes 3 in CH3CN at reflux immediately resulted in the formation of 1f, 1g and the ruthenium complex [Ru]-CH3CN (1h). Complexes 3 dissolve in CH3CN and heat from room temperature to reflux slowly to cause the formation of two compound 1f and 1h. Treatment of the vinylidene complex {Cp(PPh3)2Ru=C=CHC(Ph)2CH2C≡CH}[BF4] with an equimolar amount of the complex [M]X ([M]X = Cp(PPh3)2RuCl, Cp(PEt3)2RuCl, Cp(PPh3)2OsBr) and in the presence of AgPF6 in CH2Cl2 at room temperature afford the dinuclear vinylidene derivatives {Cp(PPh3)2Ru=C=CHC(Ph)2CH2CH=C=[M]}[PF6]2 (6a, M = Cp(PPh3)2Ru; 6b, M = Cp(PEt3)2Ru; 6c, M = Cp(PPh3)2Os). Treatment of dinuclear vinylidene complexes with NaOMe in MeOH at room temperature generated dinuclear acetylide complexes Cp(PPh3)2RuC≡CC(Ph)2CH2C≡C[M] (7a, M = Cp(PPh3)2Ru; 7b, M = Cp(PEt3)2Ru; 7c, M = Cp(PPh3)2Os) in high yield. The reaction of the terminal alkynyl group of the neutral acetylide complex Cp(PPh3)2RuC≡CC(Ph)2CH2C≡CH with an equimolar amount of the complex [M]X ([M]X = Cp(PPh3)2RuCl, Cp(PPh3)2OsBr) and AgPF6 in CH2Cl2 at room temperature affords the dinuclear vinylidene derivatives {Cp(PPh3)2RuC≡CC(Ph)2CH2CH=C=[M]}[PF6]2 (8) (8a, M = Cp(PPh3)2Ru; 8b, M = Cp(PPh3)2Os). The transformation of the neutral acetylide complex Cp(PPh3)2RuC≡CC(Ph)2CH2C≡CH in the presence of AgSbPF6 and AuPPh3Cl in CH2Cl2 give the complex {Cp(PPh3)2Ru=C=CC(Ph)2CH2CH=CH}[SbF6] (11) containing a five-membered carbocyclic ring. Treatment of complex Cp(PPh3)2RuC≡CC(Ph)2CH2C≡CH with Co2(CO)8 in benzene gives the complex Cp(PPh3)2RuC≡CC(Ph)2CH2Co2(CO)6CH (10). Additionally, transformation of the compound 1f with AgSbPF6 and AuPPh3Cl affords the corresponding bicycle compound 12.