Mechanistic Study of Nucleophilic Addition of Amine to Octahedral Iridium η1-Allenyl Leading to η3-Azatrimethylenemethane Derivatives

• Main Author: 陳玉昆
• Other Authors: 陳竹亭
• Format: Others
• Language: zh-TW
• Published: 1995
• Online Access: http://ndltd.ncl.edu.tw/handle/14031800758949910908

碩士 === 國立臺灣大學 === 化學學系 === 83 === 　　Oxidative-addition of propargyl halides to the Vaska complex yielded neutral octahedral allenyl complexes Ir(η1-CH=C=CH2)(CO)(Cl)2(PPh3)2 1a , Ir(η1-CH=C=CH2)(CO)(Br)(Cl)(PPh3)2 1b, Ir(ηCH=C=CH2)(CO)(Br)(Cl)(PPh3)2 1c. Treatment of 1b with AgOTf resulted Ir(η1-CH=C=CH2)(CO)(Cl)(PPh3)2(OTf) 2 in good yields. The reaction of 2 with ammonia or primary amines led to substltutlon yielding,｛Ir(η1-CH=C=CH2)(CO)(Cl)(PPh3)2(NH2R)}(OTf)(5a R=H, 5b R=Me, 5c R=Et,5d R=iPr, 5e R=PhCH2). Benzenesulfoamide didn't react with 2, however, the reaction of comples 2 and sodium benzenesulfoamide led to a neutral product Ir(η1-CH=C=CH2)(CO)(Cl)(PPh3)2(NHSO2Ph)7 which undergo protonation to form the ionic amine derivatives {Ir(η1-CH=C=CH2)(CO)(Cl)(PPh3)2(NH2SO2Ph)｝(CH3COO)8。 Intriguingly, aniline and its derlvatlves reacted with complex 2 to form the (η3-azatrlmethylenemethane) related species Ir(η3-CH2C(NHC6H5X)-CH2)(CO)(Cl)(PPh3)2(OTf) 9 (9a R=H, 9b R=OMe, 9c R=Me, 9d R=F, 9e R=NO2)(HN-TMM) and Ir(η3-CH2C(NRPh)CH2)(CO)(Cl)(PPh3)2(OTf) 10 (10a R=Me, 10b R=Ph). Mechanistic studies suggested that such reactlons first form aniline-substituted lonic complexes which further led to the NTMM-Irldium products. Relevant mechanistic results will be revealed.