Structure-Reactivity Relationship of Phosphinothio Zinc Complxes

• Main Authors: Cheng-chun Chao, 趙政淳
• Other Authors: Chiang, Yen-Nan
• Format: Others
• Language: zh-TW
• Published: 2009
• Online Access: http://ndltd.ncl.edu.tw/handle/thjy22

碩士 === 國立中山大學 === 化學系研究所 === 97 === We have successfully used the cadmium ion with (2-thiophenyl)phenylphosphine(PS2) or Bis(3-trimethylsilyl-2-thiophenyl)phenylphosphine(SiPS2) to synthesize [(PS2)Cd(TMEDA)](2) and [(SiPS2)Cd(TMEDA)](4) that were structurally similar to [(PS2)Zn(TMEDA)](1). We also obtained a series of zinc complxes [NEt4][(PS2)Zn(SC6H5)](6), [NEt4][{[(PS2)Zn](SC6H11)[(PS2)Zn]}](7) and [NEt4][(PS2)Zn(SCH2C6H5)](8) with systematically varied thiolates. From studying of the methylation reactions of these complexeswith methyliodine or trimethylphosphate, we found that the metal center(zinc or cadmium), ligand(PS2 or SiPS2) or the net charge (neutral ornegative) can influence the reaction time, selectivity of reaction site ormechanism. The zinc complexes (6), (7), and (8) are capable of completingthe catalytic cycle of mthylation-demethylation and hence a good model for related enzyme system.