Synthesis and Reactions of Tungsten γ-Lactones and Tungsten Trimethylenemethane Complexes

• Main Authors: Chen,Ding-Jen, 陳丁振
• Other Authors: Lin,Ying-Chih
• Format: Others
• Language: zh-TW
• Published: 1996
• Online Access: http://ndltd.ncl.edu.tw/handle/33163855574698421456

博士 === 國立臺灣大學 === 化學學系 === 84 === The tungsten γ-lactone complex CpW(CO)2[η3-CHCHC(CH3)-OC(O)] is prepared by the reaction of tungsten anion CpW(CO)3Na with 3-but- yn-2-one 。Reaction of this lactone complex with Me2NH produces a zwitterionic olefin imine complex CpW(CO)2[η2-Me2N= C(CH3)CH=CHCO 2][Me2NH2] 。Reaction of this lactone complex with MeONa affords CpW(CO)2[η3-CH3C(OCH3)CHCHCO2-Na] 。In the presence of catalytic amount of CF3COOH ， the lactone complex in CH3CN undergoes further carbonylation to form another C-C bond giving N)[η3-CHCHC(CH3)C(O)OC(O)] 。 Vinylallene tungsten cationic complex CpW(CO)2[η4-PhCH=C=C(C≡C Ph)C(=CH2)CH3]BF4 can be prepared from the reaction of CpW(CO)2[η3-CH2C(CH3)C(C≡ CPh)2] with HBF4 in CH3CN 。The reaction of this vinylallene complex with NaBH3CN affords a neutral product CpW(CO)2[η3-( CH3)2CC(C≡CPh)C=CHPh] 。Treatment of CH3)2CC(C≡CPh)C=CHPh] with CFCOOH in ether affords metal carbene complex CpW(CO)(CF3 COO)[η3-=C(CH2Ph)C(C≡CPh)=CC(CH3)2] 。