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Structure-Reactivity Relationship of Phosphinothio Zinc Complxes

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.

Identiferoai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0717109-114705
Date17 July 2009
CreatorsChao, Cheng-chun
ContributorsChang, Tsu-Hsin, Chiang, Yen-Nan, Ong, Chi-Wi
PublisherNSYSU
Source SetsNSYSU Electronic Thesis and Dissertation Archive
LanguageCholon
Detected LanguageEnglish
Typetext
Formatapplication/pdf
Sourcehttp://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0717109-114705
Rightsunrestricted, Copyright information available at source archive

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