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Chapter 1
A new chelating N,N ligand family incorporating an anilido-phosphinimine donor set has been designed. The ligand1-(NHAr)-2-(PPh2=NAr¡¦)C6H4(iPr[NN]DippH: Ar = 2,6-iPr2-C6H3, Ar¡¦ = 2,6-iPr2-C6H3; iPr [NN]MesH: Ar = 2,6-iPr2-C6H3, Ar¡¦ = 2, 4, 6-Me3C6H2; Me[NN]MesH: 2,6-Me2-C6H3, Ar¡¦ = 2, 4, 6-Me3C6H2) were synthesized via a route of reacting amido phosphine ligands with aryl azides. We observed different behaviors of adding n-BuLi in different solvents. In 31P NMR, we found the changed of chemical shift upon the different Ar¡¦ substituents. When substituent on Nphosphinimine was Dipp, there are larger chemical shift change.
Addition of [NN]H to ZnMe2 or ZnEt2 in toluene or Et2O at -35oC generated the monomeric, three-coodinate [NN]ZnR (R = Me, Et)(schem 1), while the metathesis reaction of Zn(OAc)2 with iPr[NN]DippLi(Et2O) in THF at -35oC produced iPr[NN]DippZnOAc. But in the same condition, we made the iPr[NP] iPrLi(DME) produced homoleptic {iPr[NP] iPr}2Zn. All of the complexes were characterized by multinuclear NMR spectroscopy or X-ray crystallography.
We used [NN]ZnR catalyzed ring-opening polymerization of £`-Caprolactone
. The results of catalysis had good yields in 90 to 100% and narrow PDI around 1.5. But they are not a living polymerization catalysis.
Chapter 2
We use {[NP]NiCl}2 catalyzed Kumada reactions of alkyl halide or aryl halide with Grignard reagent. In the result, Used {iPr[NP]iPr}2NiCl catalyzed aryl halide with Grignard reagent is better than other {[NP]}2NiCl, but not good catalyzed alkyl halide with Grignard reagent.
We do kinetic studies of benzene C-H bond activation by nickel complexes of amido phosphine ligand. By the result, We can defind the benzene C-H bond activation was association rection.
| Identifer | oai:union.ndltd.org:NSYSU/oai:NSYSU:etd-0706109-234730 |
| Date | 06 July 2009 |
| Creators | Tsai, Tzung-Ling |
| Contributors | Ting-Yu Lee, Liangshiu Lee, Lan-Chang Liang, Teng-Yuan Dong |
| Publisher | NSYSU |
| Source Sets | NSYSU Electronic Thesis and Dissertation Archive |
| Language | Cholon |
| Detected Language | English |
| Type | text |
| Format | application/pdf |
| Source | http://etd.lib.nsysu.edu.tw/ETD-db/ETD-search/view_etd?URN=etd-0706109-234730 |
| Rights | not_available, Copyright information available at source archive |
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